Curable compositions comprising unsaturated polyolefins

ABSTRACT

The present disclosure relates to unsaturated polyolefins and processes for preparing the same. The present disclosure further relates to curable formulations comprising the unsaturated polyolefins that show improved crosslinking.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application claims the benefit of priority to U.S.provisional application No. 62/786,100, filed on Dec. 28, 2018, which isincorporated herein by reference in its entirety.

FIELD

Embodiments relate to curable compositions that are useful for improvedcrosslinking.

BACKGROUND

Crosslinking of elastomer resins is frequently used to produce articleswith good thermomechanical properties. For example, commercial EPDMpolymers are crosslinked and used in applications across a broadtemperature range, including temperatures well above the melting pointof the uncrosslinked resin. In general, commercial polyolefins that arecrosslinked are of high molecular weight to allow for efficientcrosslinking. Alternatively, low molecular weight resins that arecrosslinkable require a high number of unsaturations. This high numberof unsaturations can result in a crosslink network with low molecularweight between crosslinks and poor thermal and UV stability because ofresidual backbone unsaturation. Moreover, crosslinking of low molecularweight (low viscosity) resins requires very high peroxide levels and, insome cases, a high gel fraction cannot be achieved, resulting in poormechanical properties. Accordingly, there is a need for a novel lowmolecular weight unsaturated polyolefin that can be crosslinkedefficiently and provides good mechanical properties, thermal and UVstability.

SUMMARY

The present disclosure relates to a curable composition comprising (A) apolyolefin component and (B) a curing component comprising across-linking agent, wherein the (A) polyolefin component comprises anunsaturated polyolefin of the formula A¹L¹, and wherein:

L¹ is a polyolefin;

-   -   A¹ is selected from the group consisting of a vinyl group, a        vinylidene group of the formula CH₂═C(Y¹)—, a vinylene group of        the formula Y¹CH═CH—, a mixture of a vinyl group and a vinylene        group of the formula Y¹CH═CH—, a mixture of a vinyl group and a        vinylidene group of the formula CH₂═C(Y¹)—, a mixture of a        vinylidene group of the formula CH₂═C(Y¹)— and a vinylene group        of the formula Y¹CH═CH—, and a mixture of a vinyl group, a        vinylidene group of the formula CH₂═C(Y¹)—, and a vinylene group        of the formula Y¹CH═CH—; and

Y¹ at each occurrence independently is a C₁ to C₃₀ hydrocarbyl group.

The present disclosure further relates to a curable compositioncomprising (A) a polyolefin component and (B) a curing componentcomprising a cross-linking agent, wherein the polyolefin componentcomprises an unsaturated polyolefin of the formula A¹L¹ and a telechelicpolyolefin of the formula A¹L¹L²A², wherein:

L¹ at each occurrence independently is a polyolefin;

A¹ at each occurrence independently is selected from the groupconsisting of a vinyl group, a vinylidene group of the formulaCH₂═C(Y¹)—, a vinylene group of the formula Y¹CH═CH—, a mixture of avinyl group and a vinylene group of the formula Y¹CH═CH—, a mixture of avinyl group and a vinylidene group of the formula CH₂═C(Y¹)—, a mixtureof a vinylidene group of the formula CH₂═C(Y¹)— and a vinylene group ofthe formula Y¹CH═CH—, and a mixture of a vinyl group, a vinylidene groupof the formula CH₂═C(Y¹)—, and a vinylene group of the formula Y¹CH═CH—;

Y¹ at each occurrence independently is a C₁ to C₃₀ hydrocarbyl group;

L² is a C₁ to C₃₂ hydrocarbylene group; and

A² is a hydrocarbyl group comprising a hindered double bond.

The curable compositions of the present disclosure may further comprise(C) an additive component.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A and 1B provide the 1H NMR and GC/MS spectra for the synthesisof CTA 1, respectively.

FIG. 2 provides the 1H NMR spectrum for the synthesis of CTA 2.

FIG. 3 provides the 1H NMR spectrum for the synthesis of a telechelicpolyolefin using CTA 7.

FIG. 4 provides the 1H NMR spectrum for the synthesis of a telechelicpolyolefin using CTA 8.

FIG. 5 provides a torque vs. time curve for certain examples.

FIG. 6 provides a torque vs. time curve for certain examples.

FIG. 7 provides a MH-ML vs. unsaturations/1000 C curve for certainexamples.

FIG. 8 provides a MH-ML vs. unsaturations/1000 C curve for certainexamples.

DETAILED DESCRIPTION Definitions

All references to the Periodic Table of the Elements herein shall referto the Periodic Table of the Elements, published and copyrighted by CRCPress, Inc., 2003. Also, any references to a Group or Groups shall be tothe Group or Groups reflected in this Periodic Table of the Elementsusing the IUPAC system for numbering groups. Unless stated to thecontrary, implicit from the context, or customary in the art, all partsand percents are based on weight. For purposes of United States patentpractice, the contents of any patent, patent application, or publicationreferenced herein are hereby incorporated by reference in their entirety(or the equivalent US version thereof is so incorporated by reference)especially with respect to the disclosure of synthetic techniques,definitions (to the extent not inconsistent with any definitionsprovided herein) and general knowledge in the art.

The numerical ranges disclosed herein include all values from, andincluding, the lower and upper value. For ranges containing explicitvalues (e.g., 1, or 2, or 3 to 5, or 6, or 7), any subrange between anytwo explicit values is included (e.g., 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5to 6; etc.). The numerical ranges disclosed herein further include thefractions between any two explicit values.

The terms “comprising,” “including,” “having” and their derivatives arenot intended to exclude the presence of any additional component, stepor procedure, whether or not the same is specifically disclosed. Inorder to avoid any doubt, all compositions claimed through use of theterm “comprising” may include any additional additive, adjuvant,component, or compound, whether polymeric or otherwise, unless stated tothe contrary. In contrast, the term “consisting essentially of” excludesfrom the scope of any succeeding recitation any other component, step,or procedure, excepting those that are not essential to operability. Theterm “consisting of” excludes any component, step, or procedure notspecifically delineated or listed. The term “or,” unless statedotherwise, refers to the listed members individually as well as in anycombination.

The term “hindered double bond” refers to a carbon-carbon double bondthat cannot readily participate in coordination polymerization. In otherwords, a hindered double bond has negligible reactivity to participatein coordination polymerization. Examples of hindered double bondsinclude but are not limited to the double bond of a vinylidene group,the double bond of a vinylene group, the double bond of a trisubstitutedalkene, and the double bond of a vinyl group attached to a branchedalpha carbon. The term “hindered double bond,” as defined herein,excludes the double bonds of strained cyclic olefins that can readilyparticipate in coordination polymerization. As one of ordinary skill inthe art would understand, examples of such strained cyclic olefinsinclude but are not limited to norbomene, ethylidene norbomene (ENB),5-vinyl-2-norbornene (VNB), dicyclopentadiene, norbomadiene,5-methylene-2-norbomene (MNB), 5-propenyl-2-norbomene,5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbomene,5-cyclohexylidene-2-norbomene, etc. The term “hindered double bond,” asdefined herein, further excludes the double bond of a vinyl groupattached to an unbranched alpha carbon.

The term “composition” refers to a mixture of materials or componentswhich comprise the composition. Accordingly, the term “a compositioncomprising” and similar terms are not intended to exclude the presenceof any additional components of the composition, whether or not the sameis specifically disclosed.

The term “acyclic” refers to a series of atoms in a polymer or compoundwhere such a series is linear or branched. Accordingly, the term“acyclic hydrocarbyl group” refers to a hydrocarbyl group that is linearor branched.

The term “cyclic” refers to a series of atoms in a polymer or compoundwhere such a series includes one or more rings. Accordingly, the term“cyclic hydrocarbyl group” refers to a hydrocarbyl group that containsone or more rings. A “cyclic hydrocarbyl group,” as used herein, maycontain acyclic (linear or branched) portions in addition to the one ormore rings.

The term “substituted” refers to a substitution of one or more hydrogenatoms with, for example, an alkyl group. The term “unsubstituted” refersto the absence of such a substitution.

The term “heteroatom,” as one of ordinary skill in the art wouldunderstand, refers to any main group atom that is not carbon orhydrogen. Suitable heteroatoms include but are not limited to nitrogen,oxygen, sulfur, phosphorus, and the halogens.

As used herein, the terms “hydrocarbyl,” “hydrocarbyl group,” and liketerms refer to compounds composed entirely of hydrogen and carbon,including aliphatic, aromatic, acyclic, cyclic, polycyclic, branched,unbranched, saturated, and unsaturated compounds.

The terms “hydrocarbyl,” “hydrocarbyl group,” “alkyl,” “alkyl group,”“aryl,” “aryl group,” “cycloalkene” and like terms are intended toinclude every possible isomer, including every structural isomer orstereoisomer. The same applies for like terms including but not limitedto heterohydrocarbyl, hydrocarbylene, heterohydrocarbylene, alkylene,heteroalkyl, heteroalkylene, arylene, heteroaryl, heteroarylene,cycloalkyl, cycloalkylene, heterocycloalkyl, and heterocycloalkylene.

The term “endocyclic double bond” refers to a double bond between twocarbon atoms that are members of a ring. The term “exocyclic doublebond” refers to a double bond between two carbon atoms where only one ofthe carbon atoms is a member of a ring.

“Active catalyst,” “active catalyst composition,” and like terms referto a transition metal compound that is, with or without a co-catalyst,capable of polymerization of unsaturated monomers. An active catalystmay be a “procatalyst” that becomes active to polymerize unsaturatedmonomers without a co-catalyst. Alternatively, an active catalyst may a“procatalyst” that becomes active, in combination with a co-catalyst, topolymerize unsaturated monomers.

The term “procatalyst” is used interchangeably with “catalyst,”“precatalyst,” “catalyst precursor,” “transition metal catalyst,”“transition metal catalyst precursor,” “polymerization catalyst,”“polymerization catalyst precursor,” “transition metal complex,”“transition metal compound,” “metal complex,” “metal compound,”“complex,” “metal-ligand complex,” and like terms.

“Co-catalyst” refers to a compound that can activate certainprocatalysts to form an active catalyst capable of polymerization ofunsaturated monomers. The term “co-catalyst” is used interchangeablywith “activator” and like terms.

“Polymer” refers to a compound prepared by polymerizing monomers,whether of the same or a different type. The generic term “polymer” thusembraces the term “homopolymer” that refers to polymers prepared fromonly one type of monomer and the terms “interpolymer” or “copolymer” asdefined herein. Trace amounts of impurities, for example, catalystresidues, may be incorporated into and/or within the polymer.

“Interpolymer” or “copolymer” refer to a polymer prepared bypolymerizing at least two different types of monomers. These genericterms include both polymers prepared from two different types ofmonomers and polymers prepared from more than two different types ofmonomers (e.g., terpolymers, tetrapolymers, etc.). These generic termsembrace all forms of interpolymers or copolymers, such as random, block,homogeneous, heterogeneous, etc.

An “ethylene-based polymer” or “ethylene polymer” is a polymer thatcontains a majority amount (greater than 50 wt %) of polymerizedethylene, based on the weight of the polymer, and, optionally, mayfurther contain polymerized units of at least one comonomer. An“ethylene-based interpolymer” is an interpolymer that contains, inpolymerized form, a majority amount (greater than 50 wt %) of ethylene,based on the weight of the interpolymer, and further containspolymerized units of at least one comonomer. Preferably, theethylene-based interpolymer is a random interpolymer (i.e., comprises arandom distribution of its monomeric constituents). An “ethylenehomopolymer” is a polymer that comprises repeating units derived fromethylene but does not exclude residual amounts of other components.

A “propylene-based polymer” or “propylene polymer” is a polymer thatcontains a majority amount (greater than 50 wt %) of polymerizedpropylene, based on the weight of the polymer, and, optionally, mayfurther contain polymerized units of at least one comonomer. A“propylene-based interpolymer” is an interpolymer that contains, inpolymerized form, a majority amount (greater than 50 wt %) of propylene,based on the weight of the interpolymer, and further containspolymerized units of at least one comonomer. Preferably, thepropylene-based interpolymer is a random interpolymer (i.e., comprises arandom distribution of its monomeric constituents). A “propylenehomopolymer” is a polymer that comprises repeating units derived frompropylene but does not exclude residual amounts of other components.

An “ethylene/alpha-olefin interpolymer” is an interpolymer that containsa majority amount (greater than 50 wt %) of polymerized ethylene, basedon the weight of the interpolymer, and further contains polymerizedunits of at least one alpha-olefin. Preferably, theethylene/alpha-olefin interpolymer is a random interpolymer (i.e.,comprises a random distribution of its monomeric constituents). An“ethylene/alpha-olefin copolymer” is a copolymer that contains amajority amount (greater than 50 wt %) of polymerized ethylene, based onthe weight of the copolymer, and further contains polymerized units ofan alpha-olefin. Preferably, the ethylene/alpha-olefin copolymer is arandom copolymer (i.e., comprises a random distribution of its monomericconstituents).

A “propylene/alpha-olefin interpolymer” is an interpolymer that containsa majority amount (greater than 50 wt %) of polymerized propylene, basedon the weight of the interpolymer, and further contains polymerizedunits of at least one alpha-olefin. Preferably, thepropylene/alpha-olefin interpolymer is a random interpolymer (i.e.,comprises a random distribution of its monomeric constituents). A“propylene/alpha-olefin copolymer” is an interpolymer that contains amajority amount (greater than 50 wt %) of polymerized propylene, basedon the weight of the copolymer, and further contains polymerized unitsof an alpha-olefin. Preferably, the propylene/alpha-olefin copolymer isa random copolymer (i.e., comprises a random distribution of itsmonomeric constituents).

“Polyolefin” refers to a polymer produced from olefin monomers, where anolefin monomer (also called an alkene) is a linear, branched, or cycliccompound of carbon and hydrogen having at least one double bond.

The terms “chain transfer agent component” and “chain transfer agent” asused herein, refers to a compound or mixture of compounds that iscapable of causing reversible or irreversible polymeryl exchange withactive catalyst sites. Irreversible chain transfer refers to a transferof a growing polymer chain from the active catalyst to the chaintransfer agent that results in termination of polymer chain growth.Reversible chain transfer refers to transfers of growing polymer chainback and forth between the active catalyst and the chain transfer agent.

The term “olefin block copolymer” or “OBC” refers to anethylene/alpha-olefin multi-block interpolymer and includes ethylene andone or more copolymerizable alpha-olefin comonomers in polymerized form,characterized by multiple blocks or segments of two or more (preferablythree or more) polymerized monomer units, the blocks or segmentsdiffering in chemical or physical properties. Specifically, the term“olefin block copolymer” refers to a polymer comprising two or more(preferably three or more) chemically distinct regions or segments(referred to as “blocks”) joined in a linear manner, that is, a polymercomprising chemically differentiated units which are joined (covalentlybonded) end-to-end with respect to polymerized functionality, ratherthan in pendent or grafted fashion. The blocks differ in the amount ortype of comonomer incorporated therein, the density, the amount ofcrystallinity, the type of crystallinity (e.g., polyethylene versuspolypropylene), the crystallite size attributable to a polymer of suchcomposition, the type or degree of tacticity (isotactic orsyndiotactic), region-regularity or region-irregularity, the amount ofbranching, including long chain branching or hyper-branching, thehomogeneity, and/or any other chemical or physical property. The blockcopolymers are characterized by unique distributions of both polymerpolydispersity (PDI or Mw/Mn) and block length distribution, e.g., basedon the effect of the use of a shuttling agent(s) in combination withcatalyst systems. Non-limiting examples of the olefin block copolymersof the present disclosure, as well as the processes for preparing thesame, are disclosed in U.S. Pat. Nos. 7,858,706 B2, 8,198,374 B2,8,318,864 B2, 8,609,779 B2, 8,710,143 B2, 8,785,551 B2, and 9,243,090B2, which are all incorporated herein by reference in their entirety.

The term “block composite” (“BC”) refers to a polymer comprising threepolymer components: (i) an ethylene-based polymer (EP) having anethylene content from 10 mol % to 90 mol % (a soft copolymer), based onthe total moles of polymerized monomer units in the ethylene-basedpolymer (EP); (ii) an alpha-olefin-based polymer (AOP) having analpha-olefin content of greater than 90 mol % (a hard copolymer), basedon the total moles of polymerized monomer units in thealpha-olefin-based polymer (AOP); and (iii) a block copolymer (diblockcopolymer) having an ethylene block (EB) and an alpha-olefin block(AOB); wherein the ethylene block of the block copolymer is the samecomposition as the EP of component (i) of the block composite and thealpha-olefin block of the block copolymer is the same composition as theAOP of component (ii) of the block composite. Additionally, in the blockcomposite, the compositional split between the amount of EP and AOP willbe essentially the same as that between the corresponding blocks in theblock copolymer. Non-limiting examples of the block composites of thepresent disclosure, as well as processes for preparing the same, aredisclosed in U.S. Pat. Nos. 8,686,087 and 8,716,400, which areincorporated herein by reference in their entirety.

The term “specified block composite” (“SBC”) refers to a polymercomprising three polymer components: (i) an ethylene-based polymer (EP)having an ethylene content from 78 mol % to 90 mol % (a soft copolymer),based on the total moles of polymerized monomer units in theethylene-based polymer (EP); (ii) an alpha-olefin-based polymer (AOP)having an alpha-olefin content of from 61 mol % to 90 mol % (a hardcopolymer), based on the total moles of polymerized monomer units in thealpha-olefin-based polymer (AOP); and (iii) a block copolymer (diblockcopolymer) having an ethylene block (EB) and an alpha-olefin block(AOB); wherein the ethylene block of the block copolymer is the samecomposition as the EP of component (i) of the specified block compositeand the alpha-olefin block of the block copolymer is the samecomposition as the AOP of component (ii) of the specified blockcomposite. Additionally, in the specified block composite, thecompositional split between the amount of EP and AOP will be essentiallythe same as that between the corresponding blocks in the blockcopolymer. Non-limiting examples of the specified block composites ofthe present disclosure, as well as processes for preparing the same, aredisclosed in WO 2017/044547, which is incorporated herein by referencein its entirety.

The term “crystalline block composite” (“CBC”) refers to polymerscomprising three components: (i) a crystalline ethylene based polymer(CEP) having an ethylene content of greater than 90 mol %, based on thetotal moles of polymerized monomer units in the crystalline ethylenebased polymer (CEP); (ii) a crystalline alpha-olefin based polymer(CAOP) having an alpha-olefin content of greater than 90 mol %, based onthe total moles of polymerized monomer units in the crystallinealpha-olefin based copolymer (CAOP); and (iii) a block copolymercomprising a crystalline ethylene block (CEB) and a crystallinealpha-olefin block (CAOB); wherein the CEB of the block copolymer is thesame composition as the CEP of component (i) of the crystalline blockcomposite and the CAOB of the block copolymer is the same composition asthe CAOP of component (ii) of the crystalline block composite.Additionally, in the crystalline block composite, the compositionalsplit between the amount of CEP and CAOP will be essentially the same asthat between the corresponding blocks in the block copolymer.Non-limiting examples of the crystalline block composites of the presentdisclosure, as well as the processes for preparing the same, aredisclosed in U.S. Pat. No. 8,822,598 B2 and WO 2016/01028961 A1, whichare incorporated herein by reference in its entirety.

The term “crystalline” refers to a polymer that possesses a first ordertransition or crystalline melting point (Tm) as determined bydifferential scanning calorimetry (DSC) or equivalent techniques. Theterm may be used interchangeably with the term “semicrystalline.” Theterm “amorphous” refers to a polymer lacking a crystalline melting pointas determined by differential scanning calorimetry (DSC) or equivalenttechnique.

(A) Polyolefin Component

In certain embodiments, the curable composition of the presentdisclosure may comprise from 80 wt % to 99.99 wt % of the (A) polyolefincomponent, based on the total weight of the curable composition.

In certain embodiments, the (A) polyolefin component comprises anunsaturated polyolefin of the formula A¹L¹. In further embodiments, the(A) polyolefin component comprises an unsaturated polyolefin of theformula A¹L¹ and a telechelic polyolefin of the formula A¹L¹L²A². Infurther embodiments, the (A) polyolefin component comprises anunsaturated polyolefin of the formula A¹L¹ and a telechelic polyolefinof the formula A¹L¹L²A², wherein the (A) polyolefin component comprisesa ratio of the unsaturated polyolefin of the formula A¹L¹ to thetelechelic polyolefin of the formula A¹L¹L²A² of from 1:99 to 99:1, orfrom 10:90 to 90:10, or from 20:80 to 80:20, or from 30:70 to 70:30, orfrom 40:60 to 60:40, or 50:50.

The (A) polyolefin component may further comprise polymers other thanthe unsaturated polyolefin of the formula A¹L¹ and the telechelicpolyolefin of the formula A¹L¹L²A², such as ethylene-based polymers.Examples of ethylene-based polymers include but are not limited toethylene/alpha-olefin copolymers, such as those available as ENGAGE™from The Dow Chemical Company, and olefin block copolymers available asINFUSE™ from The Dow Chemical Company. These ethylene/alpha-olefincopolymers and olefin block copolymers have low or no unsaturations.

As one of ordinary skill in the art would understand in view of theformula A¹L¹L²A², A¹ is covalently bonded to L¹ through a carbon-carbonsingle bond, L¹ is covalently bonded to L² through a carbon-carbonsingle bond, and L² is covalently bonded to A² through a carbon-carbonsingle bond. Accordingly, when it is stated herein that L¹ of theformula A¹L¹L²A² is a polyolefin, it is understood that L¹ is a divalentpolyolefinyl group (a polyolefin missing two hydrogens) that iscovalently bonded to each of the A¹ and L² groups through carbon-carbonsingle bonds. Likewise, when it is stated that L¹ of the formulaA¹L¹L²A² is a polymer, it is understood that L¹ is a divalent polymerylgroup (a polymer missing two hydrogens) that is covalently bonded toeach of the A¹ and L² groups through carbon-carbon single bonds. Forexample, when it is stated that L¹ is an ethylene homopolymer, it isunderstood that L¹ is a divalent ethylene homopolymeryl group (anethylene homopolymer missing two hydrogens) that is covalently bonded toeach of the A¹ and L² groups through carbon-carbon single bonds. As afurther example, when it is stated that L¹ is an ethylene/alpha-olefincopolymer, it is understood that L¹ is a divalent ethylene/alpha-olefincopolymeryl group (an ethylene/alpha-olefin copolymer missing twohydrogens) that is covalently bonded to each of the A¹ and L² groupsthrough carbon-carbon single bonds.

Similarly, as one of ordinary skill in the art would understand in viewof the formula A¹L¹, A¹ is covalently bonded to L¹ through acarbon-carbon single bond. Accordingly, wherein it is stated herein thatL¹ of the formula A¹L¹ is a polyolefin, it is understood that L¹ is apolyolefinyl group (a polyolefin missing one hydrogen) that iscovalently bonded to the A¹ group through a carbon-carbon single bond.

L¹ at each occurrence independently is a polyolefin resulting from thecoordination polymerization of unsaturated monomers (and comonomers).Examples of suitable monomers (and comonomers) include but are notlimited to ethylene and alpha-olefins of 3 to 30 carbon atoms,preferably 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene,3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene,3,5,5-trimethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,1-hexadecene, 5-ethyl-1-nonene, 1-octadecene and 1-eicosene; conjugatedor nonconjugated dienes, such as butadiene, isoprene,4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene,1,4-hexadiene, 1,3-hexadiene, 1,5-heptadiene, 1,6-heptadiene,1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene,1,7-octadiene, 1,9-decadiene, 7-methyl-1,6-octadiene,4-ethylidene-8-methyl-1,7-nonadiene, and 5,9-dimethyl-1,4,8-decatriene,5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene,3,7-dimethyl-1,7-octadiene, and mixed isomers of dihydromyrcene anddihydroocimene; norbomene and alkenyl, alkylidene, cycloalkenyl andcycloalkylidene norbomenes, such as 5-ethylidene-2-norbomene,5-vinyl-2-norbomene, dicyclopentadiene, 5-methylene-2-norbomene,5-propenyl-2-norbomene, 5-isopropylidene-2-norbomene,5-(4-cyclopentenyl)-2-norbomene, 5-cyclohexylidene-2-norbomene, andnorbornadiene; and aromatic vinyl compounds such as styrenes, mono orpoly alkylstyrenes (including styrene, o-methylstyrene, t-methylstyrene,m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene,m-ethylstyrene and p-ethylstyrene).

L¹ may be linear (unbranched), branched, or cyclic. The presence orabsence of branching in L¹, and the amount of branching (if branching ispresent), can vary widely and may depend on the desired processingconditions and the desired polymer properties. If branching is presentin L¹, the branching may be short chain branching or long chainbranching. Exemplary types of long chain branching that may be presentin L¹ include but are not limited to T-type branching and H-typebranching. Accordingly, in some embodiments, L¹ may comprise long chainbranching. In other words, in some embodiments, L¹ may comprise one ormore long chain branches, wherein each long chain branch optionallycomprises an A² group as defined herein.

In some embodiments, the A¹ group of each of the formulas A¹L¹ andA¹L¹L²A² correlates to the last inserted monomer or comonomer based onthe coordination polymerization of monomers and comonomers to form L¹.Accordingly, the selection of the monomers and comonomers for thecoordination polymerization of L¹ will indicate what the A¹ group andthe Y¹ group may be. In some embodiments, the A¹ group is a vinyl group.In some embodiments, the A¹ group is a vinylidene group of the formulaCH₂═C(Y¹)—, wherein Y¹ is a C₁ to C₃₀ hydrocarbyl group. In someembodiments, the A¹ group is a vinylene group of the formula Y¹CH═CH—,wherein Y¹ is a C₁ to C₃₀ hydrocarbyl group. In some embodiments, the A¹group is a mixture of a vinyl group and a vinylene group of the formulaY¹CH═CH—, wherein Y¹ is a C₁ to C₃₀ hydrocarbyl group. In someembodiments, the A¹ group is a mixture of a vinyl group and a vinylidenegroup of the formula CH₂═C(Y¹)—, wherein Y¹ is a C₁ to C₃₀ hydrocarbylgroup. In some embodiments, the A¹ group is a mixture of a vinylidenegroup of the formula CH₂═C(Y¹)— and a vinylene group of the formulaY¹CH═CH—, wherein Y¹ is a C₁ to C₃₀ hydrocarbyl group. In someembodiments, the A¹ group is a mixture of a vinyl group, a vinylidenegroup of the formula CH₂═C(Y¹)—, and a vinylene group of the formulaY¹CH═CH—, wherein Y¹ is a C₁ to C₃₀ hydrocarbyl group.

In further embodiments, the A¹ group is a mixture of a vinyl group and avinylene group of the formula Y¹CH═CH—, wherein A¹ comprises a ratio ofthe vinyl group to the vinylene group of the formula Y¹CH═CH— of from0.99:0.01 to 0.01:0.99, and wherein Y¹ is a C₁ to C₃₀ hydrocarbyl group.

In further embodiments, the A¹ group is a mixture of a vinyl group and avinylidene group of the formula CH₂═C(Y¹)—, wherein A¹ comprises a ratioof the vinyl group to the vinylidene group of the formula CH₂═C(Y¹)— offrom 0.99:0.01 to 0.01:0.99, and wherein Y¹ is a C₁ to C₃₀ hydrocarbylgroup.

In further embodiments, the A¹ group is a mixture of a vinylidene groupof the formula CH₂═C(Y¹)— and a vinylene group of the formula Y¹CH═CH—,wherein A¹ comprises a ratio of the vinylidene group of the formulaCH₂═C(Y¹)— to the vinylene group of the formula Y¹CH═CH— of from0.99:0.01 to 0.01:0.99, and wherein Y¹ is a C₁ to C₃₀ hydrocarbyl group.

In further embodiments, the A¹ group is a mixture of a vinyl group, avinylidene group of the formula CH₂═C(Y¹)—, and a vinylene group of theformula Y¹CH═CH—, wherein A¹ comprises a ratio of the vinyl group to thesum of the vinylene group of the formula Y¹CH═CH—, the vinylidene groupof the formula CH₂═C(Y¹)—, and the vinyl group of from 0.99:0.01 to0.01:0.99, and wherein Y¹ is a C₁ to C₃₀ hydrocarbyl group.

In certain embodiments, L¹ is a homopolymer comprising units derivedfrom one monomer. The monomer may be selected from any of the suitablemonomers discussed previously. In further embodiments, L¹ is an ethylenehomopolymer comprising units derived from ethylene. In furtherembodiments, L¹ is a propylene homopolymer comprising units derived frompropylene.

In some embodiments, L¹ is an interpolymer comprising units derived fromat least two different types of monomers, such as a monomer and acomonomer. Accordingly, in certain embodiments, L¹ is an interpolymercomprising units derived from a monomer and at least one comonomer thatis different from the monomer. Each of the monomer and the at least onecomonomer that is different from the monomer may be selected from any ofthe suitable monomers discussed previously.

In further embodiments, L¹ is a copolymer comprising units derived fromtwo different types of monomers, such as a monomer and a comonomer.Accordingly, in certain embodiments, L¹ is a copolymer comprising unitsderived from a monomer and a comonomer that is different from themonomer. Each of the monomer and the comonomer may be selected from anyof the suitable monomers discussed previously.

In certain embodiments, L¹ is an ethylene/alpha-olefin copolymer. Insome embodiments, L¹ is an ethylene/alpha-olefin copolymer comprisingunits derived from ethylene and a C₃ to C₃₀ alpha-olefin, wherein eachof the polyolefins of the formulas A¹L¹ and A¹L¹L²A² comprises an amountof ethylene that is greater than or equal to 50 wt %, or greater than orequal to 60 wt %, or greater than or equal to 70 wt %, or greater thanor equal to 75 wt %, or greater than or equal to 80 wt %, or greaterthan or equal to 85 wt %, or greater than or equal to 88 wt %, orgreater than or equal to 89 wt %, or greater than or equal to 90 wt %,based on the total weight of each of the polyolefins of the formulasA¹L¹ and A¹L¹L²A². The C₃ to C₃₀ alpha-olefin may be selected from anyof the suitable alpha-olefins discussed previously. In certainembodiments, the C₃ to C₃₀ alpha-olefin may be propylene, isobutylene,1-butene, 1-hexene, 1-pentene, 4-methyl-1-pentene, 1-heptene, 1-octene,1-nonene, 1-decene, or the like. In some embodiments, L¹ is anethylene/alpha-olefin copolymer comprising units derived from ethyleneand a C₃ to C₃₀ alpha-olefin, wherein the C₃ to C₃₀ alpha-olefin isselected from the group consisting of propylene, 1-butene, 1-hexene, and1-octene.

In further embodiments, L¹ is a propylene/alpha-olefin copolymer. L¹ maybe a propylene/alpha-olefin copolymer comprising units derived frompropylene and either ethylene or a C₄ to C₃₀ alpha-olefin, wherein eachof the polyolefins of the formulas A¹L¹ and A¹L¹L²A² comprises an amountof propylene that is greater than or equal to 50 wt %, or greater thanor equal to 60 wt %, or greater than or equal to 70 wt %, or greaterthan or equal to 75 wt %, or greater than or equal to 80 wt %, orgreater than or equal to 85 wt %, or greater than or equal to 88 wt %,or greater than or equal to 89 wt %, or greater than or equal to 90 wt%, based on the total weight of each of the polyolefins of the formulasA¹L¹ and A¹L¹L²A². The C₄ to C₃₀ alpha-olefin may be any of the suitablealpha-olefins discussed above. In certain embodiments, the C₄ to C₃₀alpha-olefin may be isobutylene, 1-butene, 1-hexene, 1-pentene,4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, or thelike. In certain embodiments, L¹ may be a propylene/alpha-olefincopolymer comprising units derived from propylene and either ethylene ora C₄ to C₃₀ alpha-olefin, wherein the C₄ to C₃₀ alpha-olefin is selectedfrom the group consisting of 1-butene, 1-hexene, and 1-octene.

In certain embodiments, L¹ is a terpolymer comprising units derived fromthree different types of monomers, each of which may be selected fromany of the suitable monomers discussed above. In further embodiments, L¹is a terpolymer comprising ethylene or propylene as a first monomer, aC₃ to C₃₀ alpha-olefin or styrene as a second monomer, and a diene orpolar monomer as a third monomer.

In some embodiments, L¹ comprises from 0 to 10 wt % of units derivedfrom diene monomers. For example, L¹ may comprise from 1 to 8 wt %, orfrom 1 to 5 wt %, or from 1 to 3 wt % of units derived from dienemonomers. In further embodiments, L¹ may be substantially free of unitsderived from diene monomers. For example, in certain embodiments, L¹ maycomprise from 0 to 0.2 wt %, or from 0 to 0.01 wt %, or from 0 to 0.001wt %, or from 0 to 0.0001 wt % of units derived from diene monomers.

In certain embodiments, L¹ is an olefin block copolymer as definedherein. In further embodiments, L¹ is a block composite, a specifiedblock composite, or a crystalline block composite as defined herein.

In certain embodiments, L² is —CH₂CH(Y²)—, such that the telechelicpolyolefin is A¹L¹CH₂CH(Y²)A², wherein Y² is hydrogen or a C₁ to C₃₀hydrocarbyl group. In certain embodiments, the Y² group is hydrogen. Infurther embodiments, the Y² group is a C₁ to C₁₀ alkyl group, or a C₁ toC₆ alkyl group, or a C₁ to C₃ alkyl group. In further embodiments, theY² group is an ethyl group.

In some embodiments, A² is a hydrocarbyl group comprising a hindereddouble bond. In further embodiments, A² is a hydrocarbyl groupcomprising two or more hindered double bonds.

In certain embodiments, due to the hindered double bond, the A² group isa group that is not readily incorporated by an active catalyst under theprocess conditions used to make the polyolefin L¹, such that directincorporation of A² along the backbone chain of L¹ is less than or equalto 0.5 mol %, or less than or equal to 0.1 mol %, or is not detected, asdetermined by the ¹³C NMR method described herein or similar ¹³C NMRmethods.

In some embodiments, A² is a hydrocarbyl group comprising a hindereddouble bond, wherein the hindered double bond is selected from the groupconsisting of the double bond of a vinylidene group, the double bond ofa vinylene group, the double bond of a trisubstituted alkene, and thedouble bond of a vinyl group attached to a branched alpha carbon.

In further embodiments, A² is a hydrocarbyl group comprising two or morehindered double bonds, wherein each hindered double bond isindependently selected from the group consisting of the double bond of avinylidene group, the double bond of a vinylene group, the double bondof a trisubstituted alkene, and the double bond of a vinyl groupattached to a branched alpha carbon.

In certain embodiments, A² is a hydrocarbyl group comprising afunctional group, wherein the functional group is selected from thegroup consisting of a vinylidene group, a vinylene group, atrisubstituted alkene, and a vinyl group attached to a branched alphacarbon.

In further embodiments, A² is a hydrocarbyl group comprising two or morefunctional groups, wherein each functional group is independentlyselected from the group consisting of a vinylidene group, a vinylenegroup, a trisubstituted alkene, and a vinyl group attached to a branchedalpha carbon.

The A² group may be a cyclic or acyclic (linear or branched) hydrocarbylgroup. If A² is a cyclic hydrocarbyl group, A² may comprise one or morerings, wherein each ring may be a monocyclic, bicyclic, or polycyclicring, and wherein each ring may comprise one or more hindered doublebonds.

Furthermore, if A² is a cyclic hydrocarbyl group, each hindered doublebond or functional group therein may be an endocyclic double bond, anexocyclic double bond, or an acyclic double bond. For example, A² may bea cyclic hydrocarbyl group comprising a vinylene group, wherein thedouble bond of the vinylene group may be an endocyclic double bond or anacyclic double bond. In further embodiments, A² may be a cyclichydrocarbyl group comprising a vinylidene group, wherein the double bondof the vinylidene group may be an exocyclic double bond or an acyclicdouble bond. In further embodiments, A² may be a cyclic hydrocarbylgroup comprising a trisubstituted alkene, wherein the double bond of thetrisubstituted alkene may be an endocyclic double bond, an exocyclicdouble bond, or an acyclic double bond. In further embodiments, A² maybe a cyclic hydrocarbyl group comprising a vinyl group attached to abranched alpha carbon, wherein the vinyl group attached to a branchedalpha carbon is an acyclic double bond.

In any of the embodiments described herein, A² may comprise from 3 to 30carbon atoms, or from 3 to 25 carbon atoms, or from 3 to 20 carbonatoms, or from 3 to 15 carbon atoms, or from 3 to 10 carbon atoms, orfrom 3 to 9 carbon atoms, or from 3 to 8 carbon atoms, or from 3 to 7carbon atoms, or from 3 to 6 carbon atoms, or from 3 to 5 carbon atoms,or from 3 to 4 carbon atoms, or 3 carbon atoms.

In certain embodiments, A² is a C₃ to C₃₀ cyclic hydrocarbyl groupcomprising an alkyl-substituted or unsubstituted cycloalkene. In furtherembodiments, A² is an alkyl-substituted or unsubstituted cycloalkenecomprising from 3 to 30 carbon atoms, or from 3 to 25 carbon atoms, orfrom 3 to 20 carbon atoms, or from 3 to 15 carbon atoms, or from 3 to 10carbon atoms, or from 3 to 9 carbon atoms, or from 3 to 8 carbon atoms,or from 3 to 7 carbon atoms, or from 3 to 6 carbon atoms.

Exemplary unsubstituted cycloalkenes include but are not limited tocyclohexene, cycloheptene, cyclooctene, 1,3-cyclohexadiene,1,4-cyclohexadiene, and 1,5-cyclooctadiene. Exemplary alkyl-substitutedcycloalkenes include but are not limited to alkyl-substitutedcyclohexene, alkyl-substituted cycloheptene, alkyl-substitutedcyclooctene, alkyl-substituted 1,3-cyclohexadiene, alkyl-substituted1,4-cyclohexadiene, and alkyl-substituted1,5-cyclooctadiene.

In some embodiments, A² is a methyl-substituted or unsubstitutedcycloalkene selected from the group consisting of a methyl-substitutedor unsubstituted cyclohexene, a methyl-substituted or unsubstitutedcycloheptene, and a methyl-substituted or unsubstituted cyclooctene. Insome embodiments, A² is a methyl-substituted or unsubstitutedcyclohexene.

In some embodiments, A² is a C₁ to C₁₀ acyclic alkyl group, or a C₃ toC₁₀ acyclic alkyl group, or a C₄ to C₈ acyclic alkyl group.

Exemplary A² groups include but are not limited to the following:

With regard to each of (AA) to (AZ) and (AZ1), the symbol (squiggly linesymbol) denotes the point of connection to L² in the formula A¹L¹L²A²,for example, the point of connection to the carbon attached to ahydrogen, “Y²,” and “A¹L¹CH₂” in the formula A¹L¹CH₂CH(Y²)A². Inaddition, with regard to each of (AA) to (AZ) and (AZ1), the symbol(squiggly line symbol) denotes the point of connection to the carbonattached to a hydrogen and Y² in the chain transfer agent formulas ofAl(CH₂CH(Y²)A²)₃ and Zn(CH₂CH(Y²)A²)₂ discussed below.

With regard to each of (AA) to (AF), the endocyclic double bond may bebetween any two adjacent carbon atoms that are ring members.

With regard to each of (AD) to (AF), the pendant methyl group may beconnected to any carbon atom that is a ring member.

With regard to each of (AG) to (AL), the exocyclic double bond may beconnected to any ring member carbon atom that is not already connectedto more than two carbon atoms.

In some embodiments, the (A) polyolefin component (or each of thepolyolefins of the formulas A¹L¹ and A¹L¹L²A²) comprises or has, inaccordance with the GPC method described herein or similar GPC methods,a weight average molecular weight (Mw) of from 1,000 to 10,000,000g/mol, or from 1,000 to 5,000,000 g/mol, or from 1,000 to 1,000,000g/mol, or from 1,000 to 750,000 g/mol, or from 1,000 to 500,000 g/mol,or from 1,000 to 250,000 g/mol.

In some embodiments, the (A) polyolefin component (or each of thepolyolefins of the formulas A¹L¹ and A¹L¹L²A²) comprises or has, inaccordance with the GPC method described herein or similar GPC methods,a number average molecular weight (Mn) of from 1,000 to 10,000,000g/mol, or from 1,000 to 5,000,000 g/mol, or from 1,000 to 1,000,000g/mol, or from 1,000 to 750,000 g/mol, or from 1,000 to 500,000 g/mol,or from 1,000 to 250,000 g/mol.

In some embodiments, the (A) polyolefin component (or each of thepolyolefins of the formulas A¹L¹ and A¹L¹L²A²) comprises or has, inaccordance with the GPC method described herein or similar GPC methods,an average molar mass (Mz) of from 1,000 to 10,000,000 g/mol, or from1,000 to 5,000,000 g/mol, or from 1,000 to 1,000,000 g/mol, or from1,000 to 750,000 g/mol, or from 1,000 to 500,000 g/mol, or from 5,000 to500,000 g/mol, or from 10,000 to 500,000 g/mol.

In some embodiments, the (A) polyolefin component (or each of thepolyolefins of the formulas A¹L¹ and A¹L¹L²A²) comprises or has, inaccordance with the GPC method described herein or similar GPC methods,a Mw/Mn (PDI) of from 1 to 10, or from 1 to 7, or from 1 to 5, or from1.5 to 4, or from 2 to 4.

In some embodiments, the (A) polyolefin component (or each of thepolyolefins of the formulas A¹L¹ and A¹L¹L²A²) comprises or has, inaccordance with ASTM D-792, Method B, a density of from 0.850 to 0.965g/cc, or from 0.854 to 0.950 g/cc, or from 0.854 to 0.935 g/cc, or from0.854 to 0.925 g/cc, or from 0.854 to 0.910 g/cc, or from 0.854 to 0.900g/cc, or from 0.854 to 0.885 g/cc, or from 0.854 to 0.880 g/cc, or from0.854 to 0.875 g/cc.

In some embodiments, the (A) polyolefin component (or each of thepolyolefins of the formulas A¹L¹ and A¹L¹L²A²) comprises or has, inaccordance with ASTM D-1238, condition 190° C./2.16 kg, a melt index(I2) of from 0.01 to 2000 g/10 minutes, or from 0.01 to 1,500 g/10minutes, or from 0.01 to 1,000 g/10 minutes, or from 0.01 to 500 g/10minutes, or from 0.01 to 100 g/10 minutes, or from 0.5 to 50 g/10minutes, or from 0.5 to 30 g/10 minutes.

In some embodiments, the (A) polyolefin component (or each of thepolyolefins of the formulas A¹L¹ and A¹L¹L²A²) comprises or has, inaccordance with the DSC method described herein or similar DSC methods,a T_(m) in the range of from −25° C. to 165° C., or from −25° C. to 150°C., or from −25° C. to 125° C., or from −25° C. to 100° C., or from 0°C. to 80° C., or from 10° C. to 60° C.

In some embodiments, the (A) polyolefin component (or each of thepolyolefins of the formulas A¹L¹ and A¹L¹L²A²) comprises or has, inaccordance with ASTM D-3236, a Brookfield viscosity (as measured at 177°C.) of from 10 to 10⁸ cP, or from 10 to 10⁷ cP, or from 10 to 10⁶ cP, orfrom 10 to 750,000 cP, or from 10 to 500,000 cP, or from 10 to 250,000cP, or from 10 to 100,000 cP, or from 10 to 75,000 cP, or from 10 to50,000 cP, or from 10 to 40,000 cP.

In some embodiments, the (A) polyolefin component (or each of thepolyolefins of the formulas A¹L¹ and A¹L¹L²A²) comprises or has, inaccordance with the DSC method described herein or similar DSC methods,an enthalpy of melting (ΔHm) of from 0 to 235 J/g, or from 0 to 200 J/g,or from 10 to 175 J/g, or from 10 to 150 J/g, or from 10 to 125 J/g, orfrom 20 to 117 J/g.

In some embodiments, the (A) polyolefin component (or each of thepolyolefins of the formulas A¹L¹ and A¹L¹L²A²) comprises or has, inaccordance with the DSC method described herein or similar DSC methods,a wt % crystallinity of from 0 to 80%, or from 0 to 60%, or from 5 to50%, or from 7 to 40%, based on PE ΔHm of 292 J/g.

In some embodiments, the (A) polyolefin component (or each of thepolyolefins of the formulas A¹L¹ and A¹L¹L²A²) comprises or has, inaccordance with the DSC method described herein or similar DSC methods,a T_(g) of from −80 to 100° C., or from −80 to 75° C., or from −80 to50° C., or from −80 to 25° C., or from −80 to 0° C., or from −80 to −15°C., or from −70 to −30° C.

In some embodiments, L¹ is substantially free of units derived fromdiene monomers, and the polyolefin of the formula A¹L¹ comprises a totalnumber of unsaturations of equal to or greater than 0.6, or equal to orgreater than 0.7, or equal to or greater than 0.8, or equal to orgreater than 0.9, or equal to or greater than 1.0, or equal to orgreater than 1.1, or equal to or greater than 1.2, or equal to orgreater than 1.3; and the polyolefin of the formula A¹L¹L²A² comprises atotal number of unsaturations of equal to or greater than 1.1, or equalto or greater than 1.2, or equal to or greater than 1.3, or equal to orgreater than 1.4, or equal to or greater than 1.5, or equal to orgreater than 1.6, or equal to or greater than 1.7, or equal to orgreater than 1.8, or equal to or greater than 1.9. The total number ofunsaturations may be defined as (unsaturations/1000 C)*(1000C/chain)=(unsaturations/1000 C)*(Mn/M_(CH2)/1000), whereunsaturations/1000 C is measured by ¹H NMR, Mn is the number averagemolecular weight as measured by GPC and corrected for composition asmeasured by ¹³C NMR, M_(CH2)=14 g/mol. As reported, Mn measured by GPCis the polymer backbone number average molecular weight.Unsaturations/1000 C as measured by 1H NMR is relative to total carbonsin the polymer chain. For ethylene, propylene, octene, and ethylidenenorbornene there are 2, 3, 8, and 9 total carbon atoms respectively, per2 backbone carbon atoms. Therefore, the Mn corrected for composition isMn as measured by GPC times (mol % C2/2+mol % C3/3+mol % C_(8/8)+mol %ENB/9)/2. ¹³C NMR, ¹H NMR, and GPC here refer to the methods describedherein or similar methods. “Substantially free,” as used here, refersto, for example, L¹ comprising from 0 to 0.001 wt % of units derivedfrom diene monomers, based on the total weight of each of thepolyolefins of the formulas A¹L¹ and A¹L¹L²A².

In some embodiments, L¹ comprises from 1 to 8 wt %, or from 1 to 5 wt %,or from 1 to 3 wt % of units derived from diene monomers, based on thetotal weight of each of the polyolefins of the formulas A¹L¹ andA¹L¹L²A², and the polyolefin of the formula A¹L¹ comprises a totalnumber of unsaturations of equal to or greater than (XD+0.6), equal toor greater than (XD+0.7), equal to or greater than (XD+0.8), equal to orgreater than (XD+0.9), equal to or greater than (XD+1), equal to orgreater than (XD+1.1), equal to or greater than (XD+1.2), or equal to orgreater than (XD+1.3), and the polyolefin of the formula A¹L¹L²A²comprises a total number of unsaturations of equal to or greater than(XD+1.1), equal to or greater than (XD+1.2), equal to or greater than(XD+1.3), equal to or greater than (XD+1.4), equal to or greater than(XD+1.5), equal to or greater than (XD+1.6), equal to or greater than(XD+1.7), equal to or greater than (XD+1.8), or equal to or greater than(XD+1.9), wherein XD is the number of unsaturations from the unitsderived from diene monomers in L¹, and wherein unsaturations aremeasured as described in the previous paragraph.

Preparing the (A) Polyolefin Component

The present disclosure further relates to a process for preparing apolyolefin component comprising an unsaturated polyolefin of the formulaA¹L¹, the process comprising:

1) combining starting materials comprising (al) a monomer component,(b1) a chain transfer agent component, and (c1) a catalyst componentcomprising a procatalyst to form a solution and polymerizing fromgreater than 10 mol % to less than or equal to 99 mol % of the (a1)monomer component in the solution;

2) heating the solution to a temperature of at least 160° C. and holdingthe solution at the temperature of at least 160° C. for a time of atleast 30 seconds; and

3) recovering a product comprising the polyolefin component comprisingthe unsaturated polyolefin of the formula A¹L¹, wherein:

the (b1) chain transfer agent component comprises an aluminum alkyl ofthe formula Al(d)₃, and

d at each occurrence independently is a C₁ to C₁₀ alkyl group

L¹ is a polyolefin;

A¹ is selected from the group consisting of a vinyl group, a vinylidenegroup of the formula CH₂═C(Y¹)—, a vinylene group of the formulaY¹CH═CH—, a mixture of a vinyl group and a vinylene group of the formulaY¹CH═CH—, a mixture of a vinyl group and a vinylidene group of theformula CH₂═C(Y¹)—, a mixture of a vinylidene group of the formulaCH₂═C(Y¹)— and a vinylene group of the formula Y¹CH═CH—, and a mixtureof a vinyl group, a vinylidene group of the formula CH₂═C(Y¹)—, and avinylene group of the formula Y¹CH═CH—;

Y¹ at each occurrence independently is a C₁ to C₃₀ hydrocarbyl group;and

the unsaturated polyolefin of the formula A¹L¹ comprises a weightaverage molecular weight from 1,000 to 10,000,000 g/mol.

The present disclosure further relates to a process for preparing apolyolefin component comprising a polyolefin of the formula A¹L¹ and atelechelic polyolefin of the formula A¹L¹L²A², the process comprising:

1) combining starting materials comprising (al) a monomer component,(b1) a chain transfer agent component, and (c1) a catalyst componentcomprising a procatalyst to form a solution and polymerizing fromgreater than 10 mol % to less than or equal to 99 mol % of the (A)monomer component in the solution;

2) heating the solution to a temperature of at least 160° C. and holdingthe solution at the temperature of at least 160° C. for a time of atleast 30 seconds; and

3) recovering a product comprising the polyolefin component comprisingthe polyolefin of the formula A¹L¹ and the telechelic polyolefin of theformula A¹L¹L²A², wherein:

the (b1) chain transfer agent component comprises an aluminum alkyl ofthe formula Al(d)₃ and an organoaluminum compound of the formulaAl(CH₂CH(Y²)A²)₃;

d at each occurrence independently is a C₁ to C₁₀ alkyl group;

L¹ at each occurrence independently is a polyolefin;

A¹ at each occurrence independently is selected from the groupconsisting of a vinyl group, a vinylidene group of the formulaCH₂═C(Y¹)—, a vinylene group of the formula Y¹CH═CH—, a mixture of avinyl group and a vinylene group of the formula Y¹CH═CH—, a mixture of avinyl group and a vinylidene group of the formula CH₂═C(Y¹)—, a mixtureof a vinylidene group of the formula CH₂═C(Y¹)— and a vinylene group ofthe formula Y¹CH═CH—, and a mixture of a vinyl group, a vinylidene groupof the formula CH₂═C(Y¹)—, and a vinylene group of the formula Y¹CH═CH—;

Y¹ at each occurrence independently is a C₁ to C₃₀ hydrocarbyl group;and

L² is a C₁ to C₃₂ hydrocarbylene group;

Y² at each occurrence independently is hydrogen or a C₁ to C₃₀hydrocarbyl group;

A² at each occurrence independently is a hydrocarbyl group comprising ahindered double bond; and

each of the unsaturated polyolefin of the formula A¹L¹ and thetelechelic polyolefin of the formula A¹L¹L²A² comprises a weight averagemolecular weight from 1,000 to 10,000,000 g/mol.

For the process of preparing a polyolefin component comprising anunsaturated polyolefin of the formula A¹L¹ and a telechelic polyolefinof the formula A¹L¹L²A², the (b1) chain transfer agent component maycomprise a ratio of the aluminum alkyl of the formula Al(d)₃ to theorganoaluminum compound of the formula Al(CH₂CH(Y²)A²)₃ from 1:99 to99:1, or from 10:90 to 90:10, or from 20:80 to 80:20, or from 30:70 to70:30, or from 40:60 to 60:40, or 50:50. Each of the unsaturatedpolyolefin of the formula A¹L¹ and the telechelic polyolefin of theformula A¹L¹L²A² prepared by the above processes may comprise a weightaverage molecular weight from 1,000 to 10,000,000 g/mol, or from 1,000to 5,000,000 g/mol, or from 1,000 to 1,000,000 g/mol, or from 1,000 to750,000 g/mol, or from 1,000 to 500,000 g/mol. Polymers other than theunsaturated polyolefin of the formula A¹L¹ and the telechelic polyolefinof the formula A¹L¹L²A² that are suitable for inclusion in the (A)polyolefin component (discussed below) may be prepared independentlyfrom the above processes and subsequently blended with the unsaturatedpolyolefin of the formula A¹L¹ and/or the telechelic polyolefin of theformula A¹L¹L²A².

The previously described embodiments for each of the L¹, A¹, Y¹, L², Y²,and A² groups apply with respect to the present processes disclosedherein. Similarly, the previously described embodiments for theunsaturated polyolefin of the formula A¹L¹ and the telechelic polyolefinof the formula A¹L¹L²A² apply with respect to the present processesdisclosed herein.

The starting materials in step 1) of any of the above processes mayfurther comprise a (d1) solvent. The (d1) solvent of the startingmaterials may be any aromatic or aliphatic hydrocarbon. Suitablesolvents include but are not limited to toluene, xylene, hexane,pentane, benzene, heptane, Isopar™, and combinations thereof. Beyondthis, the starting materials in step 1) may further comprise hydrogen,adjuvants, scavengers, and/or polymerization aids.

Step 1) of any of the above processes is a coordination polymerizationstep to form L¹ from the monomers and comonomers of the (a1) monomercomponent. During step 1), polymeryl aluminum species can form via chaintransfer between the (b1) chain transfer agent component and an activecatalyst from the (c1) catalyst component. Subsequently, the polymerylaluminum species undergo beta-hydride elimination during step 2) to forma product comprising the unsaturated polyolefin of the formula A¹L¹and/or the telechelic polyolefin of the formula A¹L¹L²A² of the (A)polyolefin component, which is recovered during step 3).

Step 1) of any of the above processes is preferably carried out as asolution polymerization step. Most preferably, step 1) is performed as acontinuous solution polymerization step in which the starting materialsare continuously supplied to a reaction zone and polymer products arecontinuously removed therefrom. Within the scope of the terms“continuous” and “continuously,” as used in this context, are thoseprocesses in which there are intermittent additions of reactants andremoval of products at regular or irregular intervals, so that, overtime, the overall process is substantially continuous.

Step 1) of any of the above processes may be performed at a temperaturefrom 60° C., or 80° C., or 100° C., or 110° C., or 115° C. to 120° C.,or 130° C., or 140° C., or 150° C. For example, in certain embodiments,step 1) may be performed at a temperature from 60 to 150° C., or from 80to 140° C., or from 100 to 130° C.

One of ordinary skill in the art would understand that the amounts ofeach component of the starting materials, including components (a1) to(d1), may be varied in order to produce polymers differing in one ormore chemical or physical properties.

Without limiting in any way the scope of the invention, one means forcarrying out step 1) is as follows. In a stirred-tank reactor, themonomers of the (a1) monomer component are introduced continuouslytogether with any solvent or diluent. The reactor contains a liquidphase composed substantially of monomers together with any solvent ordiluent and dissolved polymer. Preferred solvents include C₄₋₁₀hydrocarbons or mixtures thereof, especially alkanes such as hexane ormixtures of alkanes, as well as one or more of the monomers employed inthe polymerization. The (b1) chain transfer agent component and the (c1)catalyst component are continuously or intermittently introduced in thereactor liquid phase or any recycled portion thereof. The reactortemperature and pressure may be controlled by adjusting thesolvent/monomer ratio, the addition rate of the (c1) catalyst component,as well as by cooling or heating coils, jackets or both. Thepolymerization rate is controlled by the rate of addition of the (c1)catalyst component. If the (a1) monomer component comprises ethylene andat least one comonomer, the ethylene content of the polymer product isdetermined by the ratio of ethylene to comonomer in the reactor, whichis controlled by manipulating the respective feed rates of thesecomponents to the reactor. The polymer product molecular weight iscontrolled, optionally, by controlling other polymerization variablessuch as the temperature, monomer concentration, or others known in theart. In a continuous process, the mean residence time of the activecatalyst and polymer in the reactor generally is from 5 minutes to 8hours, and preferably from 10 minutes to 6 hours.

Alternatively, step 1) of any of the above processes may be conductedunder differentiated process conditions in two or more reactors,connected in series, operating under steady state polymerizationconditions or in two or more zones of a reactor operating under plugflow polymerization conditions. Alternatively, step 1) of any of theabove processes may be conducted in one or more continuous loop reactorswith or without monomer, catalyst, or chain transfer agent gradientsestablished between differing regions thereof, optionally accompanied byseparated addition of catalysts and/or chain transfer agent, andoperating under adiabatic or non-adiabatic solution polymerizationconditions or combinations of the foregoing reactor conditions.

Following step 1), the polymer solution is heated in accordance withstep 2), as further described below. Such heating includes, but is notlimited to, heating in a post-reactor heater. Following step 2), thepolymer product is recovered in step 3) by means known in the art. Suchmeans include contacting the polymer solution with a catalyst kill agentsuch as water, steam or an alcohol, flashing off gaseous monomers aswell as residual solvent or diluent at reduced pressure, and, ifnecessary, conducting further devolatilization in equipment such as adevolatilizing extruder.

In some embodiments, the solution in step 2) of any of the aboveprocesses is heated at a temperature of at least 160° C., or at least180° C., or at least 200° C., or at least 210° C., or at least 220° C.,or at least 230° C., or at least 240° C., or at least 250° C., or atleast 260° C., or at least 270° C., or at least 280° C., or at least290° C., or at least 300° C.

In some embodiments, the solution in step 2) of any of the aboveprocesses is heated at a temperature of at least 160° C., or at least180° C., or at least 200° C., or at least 210° C., or at least 220° C.,or at least 230° C., or at least 240° C., or at least 250° C., or atleast 260° C., or at least 270° C., or at least 280° C., or at least290° C., or at least 300° C. for a time of at least 30 seconds, or atleast 1 minute, or at least 5 minutes, or at least 10 minutes, or atleast 15 minutes, or at least 20 minutes, or at least 30 minutes, or atleast 45 minutes, or at least 1 hour, or at least 6 hours, or least 12hours, or at least 18 hours, or at least 24 hours

In some embodiments, the solution in step 2) of any of the aboveprocesses is heated to a temperature of at least 160° C., or at least180° C., or at least 200° C., or at least 210° C., or at least 220° C.,or at least 230° C., or at least 240° C., or at least 250° C., or atleast 260° C., or at least 270° C., or at least 280° C., or at least290° C., or at least 300° C. and held at a temperature of at least 160°C., or at least 180° C., or at least 200° C., or at least 210° C., or atleast 220° C., or at least 230° C., or at least 240° C., or at least250° C., or at least 260° C., or at least 270° C., or at least 280° C.,or at least 290° C., or at least 300° C. for a time of at least 30seconds, or at least 1 minute, or at least 5 minutes, or at least 10minutes, or at least 15 minutes, or at least 20 minutes, or at least 30minutes, or at least 45 minutes, or at least 1 hour, or at least 6hours, or least 12 hours, or at least 18 hours, or at least 24 hours.

For example, in certain embodiments, the solution in step 2) of any ofthe above processes is heated at a temperature from 160 to 300° C., orfrom 180 to 300° C., or from 200 to 300° C., or from 210 to 300° C., orfrom 220 to 290° C., or from 230 to 290° C., or from 240 to 280° C.

In further embodiments, the solution in step 2) of any of the aboveprocesses is heated at a temperature from 160 to 300° C., or from 180 to300° C., or from 200 to 300° C., or from 210 to 300° C., or from 220 to290° C., or from 230 to 290° C., or from 240 to 280° C. for a time from30 seconds to 24 hours, or from 30 seconds to 18 hours, or from 30seconds to 12 hours, or from 30 seconds to 6 hours, or from 30 secondsto 1 hour, or from 30 seconds to 45 minutes, or from 30 seconds to 30minutes, or from 30 seconds to 20 minutes, or from 1 minute to 20minutes, or from 5 minutes to 20 minutes.

In further embodiments, the solution in step 2) of any of the aboveprocesses is heated to a temperature from 160 to 300° C., or from 180 to300° C., or from 200 to 300° C., or from 210 to 300° C., or from 220 to290° C., or from 230 to 290° C., or from 240 to 280° C. and held at atemperature from 160 to 300° C., or from 180 to 300° C., or from 200 to300° C., or from 210 to 300° C., or from 220 to 290° C., or from 230 to290° C., or from 240 to 280° C. for a time from 30 seconds to 24 hours,or from 30 seconds to 18 hours, or from 30 seconds to 12 hours, or from30 seconds to 6 hours, or from 30 seconds to 1 hour, or from 30 secondsto 45 minutes, or from 30 seconds to 30 minutes, or from 30 seconds to20 minutes, or from 1 minute to 20 minutes, or from 5 minutes to 20minutes.

The (a1) Monomer Component

The (a1) monomer component comprises any monomer selected from themonomers and comonomers discussed herein with regard to L¹. Examples ofsuitable monomers and comonomers include but are not limited to ethyleneand alpha-olefins of 3 to 30 carbon atoms, preferably 3 to 20 carbonatoms, such as propylene, 1-butene, 1-pentene, 3-methyl-1-butene,1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene,3,5,5-trimethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene,1-hexadecene, 5-ethyl-1-nonene, 1-octadecene and 1-eicosene; conjugatedor nonconjugated dienes, such as butadiene, isoprene,4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene,1,4-hexadiene, 1,3-hexadiene, 1,5-heptadiene, 1,6-heptadiene,1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene,1,7-octadiene, 1,9-decadiene, 7-methyl-1,6-octadiene,4-ethylidene-8-methyl-1,7-nonadiene, and 5,9-dimethyl-1,4,8-decatriene,5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene,3,7-dimethyl-1,7-octadiene, and mixed isomers of dihydromyrcene anddihydroocimene; norbornene and alkenyl, alkylidene, cycloalkenyl andcycloalkylidene norbornenes, such as 5-ethylidene-2-norbornene,5-vinyl-2-norbornene, dicyclopentadiene, 5-methylene-2-norbornene,5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene,5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene, andnorbornadiene; aromatic vinyl compounds such as styrenes, mono or polyalkylstyrenes (including styrene, o-methylstyrene, t-methylstyrene,m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene,m-ethylstyrene and p-ethylstyrene).

In some embodiments, the (a1) monomer component comprises ethylenemonomers. In some embodiments, the (a1) monomer component comprisespropylene monomers. In some embodiments, the (a1) monomer componentcomprises ethylene monomers and comonomers of a C3 to C30 alpha-olefin.The C3 to C30 alpha olefin may be selected from propylene, 1-butene,1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene,3-methyl-1-pentene, 3,5,5-trimethyl-1-hexene, 1-octene, 1-decene,1-dodecene, 1-tetradecene, 1-hexadecene, 5-ethyl-1-nonene, 1-octadeceneand 1-eicosene. In some embodiments, the (a1) monomer componentcomprises propylene monomers and comonomers of ethylene or a C4 to C30alpha-olefin. The C4 to C30 alpha-olefin may be selected from 1-butene,1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene,3-methyl-1-pentene, 3,5,5-trimethyl-1-hexene, 1-octene, 1-decene,1-dodecene, 1-tetradecene, 1-hexadecene, 5-ethyl-1-nonene, 1-octadeceneand 1-eicosene.

In certain embodiments, the (a1) monomer component comprises ethylenemonomers and comonomers of a C3 to C30 alpha-olefin, wherein the C3 toC30 alpha-olefin is selected from the group consisting of propylene,1-hexene, 1-butene, and 1-octene. In further embodiments, the (a1)monomer component comprises ethylene monomers and propylene comonomers.In further embodiments, the (a1) monomer component comprises ethylenemonomers and 1-hexene comonomers. In further embodiments, the (a1)monomer component comprises ethylene monomers and 1-butene comonomers.In further embodiments, the (a1) monomer component comprises ethylenemonomers and 1-octene comonomers.

In further embodiments, the (a1) monomer component comprises propylenemonomers and comonomers of ethylene or a C4 to C30 alpha-olefin, whereinthe C4 to C30 alpha-olefin is selected from the group consisting of1-hexene, 1-butene, and 1-octene. In further embodiments, the (a1)monomer component comprises propylene monomers and ethylene comonomers.In further embodiments, the (a1) monomer component comprises propylenemonomers and 1-hexene comonomers. In further embodiments, the (a1)monomer component comprises propylene monomers and 1-butene comonomers.In further embodiments, the (a1) monomer component comprises propylenemonomers and 1-octene comonomers.

In certain embodiments, the (a1) monomer component comprises fromgreater than or equal to 50 wt % to less than or equal to 99 wt % (e.g.,from greater than or equal to 60 wt % to less than or equal to 99 wt %,or from greater than or equal to 70 wt % to less than or equal to 99 wt%, or from greater than or equal to 75 wt % to less than or equal to 99wt %, or from greater than or equal to 80 wt % to less than or equal to99 wt %, or from greater than or equal to 85 wt % to less than or equalto 99 wt %, or from greater than or equal to 90 wt % to less than orequal to 99 wt %) of ethylene monomers and from greater than or equal to1 wt % to less than or equal to 50 wt % (e.g., from greater than orequal to 1 wt % to less than or equal to 40 wt %, or from greater thanor equal to 1 wt % to less than or equal to 30 wt %, or from greaterthan or equal to 1 wt % to less than or equal to 25 wt %, or fromgreater than or equal to 1 wt % to less than or equal to 20 wt %, orfrom greater than or equal to 1 wt % to less than or equal to 15 wt %,or from greater than or equal to 1 wt % to less than or equal to 10 wt%) of comonomers of a C3 to C30 alpha-olefin, wherein the C₃ to C₃₀alpha-olefin is selected from the group consisting of propylene,1-hexene, 1-butene, and 1-octene.

In certain embodiments, the (a1) monomer component comprises fromgreater than or equal to 50 wt % to less than or equal to 99 wt % (e.g.,from greater than or equal to 60 wt % to less than or equal to 99 wt %,or from greater than or equal to 70 wt % to less than or equal to 99 wt%, or from greater than or equal to 75 wt % to less than or equal to 99wt %, or from greater than or equal to 80 wt % to less than or equal to99 wt %, or from greater than or equal to 85 wt % to less than or equalto 99 wt %, or from greater than or equal to 90 wt % to less than orequal to 99 wt %) of propylene monomers and from greater than or equalto 1 wt % to less than or equal to 50 wt % (e.g., from greater than orequal to 1 wt % to less than or equal to 40 wt %, or from greater thanor equal to 1 wt % to less than or equal to 30 wt %, or from greaterthan or equal to 1 wt % to less than or equal to 25 wt %, or fromgreater than or equal to 1 wt % to less than or equal to 20 wt %, orfrom greater than or equal to 1 wt % to less than or equal to 15 wt %,or from greater than or equal to 1 wt % to less than or equal to 10 wt%) of comonomers of ethylene or a C4 to C30 alpha-olefin, wherein the C4to C30 alpha-olefin is selected from the group consisting of 1-hexene,1-butene, and 1-octene.

In some embodiments, the (a1) monomer component comprises from 0 to 10wt % of diene monomers. For example, the (a1) monomer component maycomprise from 0.5 to 8 wt %, or from 1 to 5 wt %, or from 1 to 3 wt % ofdiene monomers. In further embodiments, the (a1) monomer component maybe substantially free of diene monomers. For example, in certainembodiments, the (a1) monomer component may comprise from 0 to 0.2 wt %,or from 0 to 0.01 wt %, or from 0 to 0.001 wt %, or from 0 to 0.0001 wt% of diene monomers.

The (b1) Chain Transfer Agent

The (b1) chain transfer agent component may comprise any chain transferagent described herein or disclosed in U.S. provisional application Nos.62/786,084, 62/786,100, 62/786,119, and 62/786,110.

The aluminum alkyl of the formula Al(d)₃ may be a tri(C₁₋₈) alkylaluminum. Non-limiting examples of the aluminum alkyl of the formulaAl(d)₃ are triethyl aluminum, tri(i-propyl) aluminum, tri(i-butyl)aluminum, tri(n-hexyl) aluminum, and tri(n-octyl) aluminum.

Without being bound by any particular theory, the aluminum alkyl of theformula Al(d)₃ contributes to the formation of the unsaturatedpolyolefin of the formula A¹L¹ while organoaluminum compound of theformula Al(CH₂CH(Y²)A²)₃ contributes to the formation of the telechelicpolyolefin of the formula A¹L¹L²A².

In certain embodiments, the (b1) chain transfer agent componentcomprises an organoaluminum compound of the formula Al(CH₂CH(Y²)A²)₃,wherein: Y² at each occurrence independently is hydrogen or a C₁ to C₃₀hydrocarbyl group; and A² at each occurrence independently is ahydrocarbyl group comprising a hindered double bond. In furtherembodiments, the (b1) chain transfer agent component is theorganoaluminum compound of the formula Al(CH₂CH(Y²)A²)₃. Y² and A² maybe any of the previously described embodiments. In certain embodiments,Y² of the organoaluminum compound of the formula Al(CH₂CH(Y²)A²)₃ may beselected from the group consisting of hydrogen, a methyl group, and anethyl group. In certain embodiments, A² of the organoaluminum compoundof the formula Al(CH₂CH(Y²)A²)₃ may be selected from among (AA) to (AZ)and (AZ1) discussed previously. In further embodiments, A² of theorganoaluminum compound of the formula Al(CH₂CH(Y²)A²)₃ is selected fromthe group consisting of (AC), (AF), (AM), (AO), (AP), (AS), and (AZ1).The pendant methyl group of (AF) may be connected to any carbon atomthat is a ring member.

The organoaluminum compound of the formula Al(CH₂CH(Y²)A²)₃ may beprepared by a thermal process comprising: (a) combining startingmaterials comprising a hydrocarbon of the formula CH₂═C(Y²)A², analuminum alkyl of the formula Al(d)₃, and an optional solvent to form anorganoaluminum solution, (b) heating the organoaluminum solution to atemperature from 60 to 200° C., or from 80 to 180° C., or from 100 to150° C., or from 110 to 130° C. and holding the organo-aluminum solutionat the temperature of from 60 to 200° C., or from 80 to 180° C., or from100 to 150° C., or from 110 to 130° C. for a time from 30 minutes to 200hours, or from 30 minutes to 100 hours, or from 30 minutes to 50 hours,or from 30 minutes to 25 hours, or from 1 hour to 10 hours, or from 1hour to 5 hours, or from 3 hours to 5 hours, and (c) recovering aproduct comprising the organoaluminum compound of the formulaAl(CH₂CH(Y²)A²)₃, wherein: d at each occurrence independently is a C₁ toC₁₀ alkyl group; Y² at each occurrence independently is hydrogen or a C₁to C₃₀ hydrocarbyl group; and A² at each occurrence independently is ahydrocarbyl group comprising a hindered double bond. In certainembodiments, the carbon of d that is attached to Al is a carbon that isconnected to a tertiary carbon. For example, in certain embodiments, thealuminum alkyl of the formula Al(d)₃ is triisobutylaluminum. In certainembodiments, in step (b), the organoaluminum solution is heated at atemperature from 60 to 200° C., or from 80 to 180° C., or from 100 to150° C., or from 110 to 130° C. In further embodiments, in step (b), theorganoaluminum solution is heated at a temperature from 60 to 200° C.,or from 80 to 180° C., or from 100 to 150° C., or from 110 to 130° C.for a time from 30 minutes to 200 hours, or from 30 minutes to 100hours, or from 30 minutes to 50 hours, or from 30 minutes to 25 hours,or from 1 hour to 10 hours, or from 1 hour to 5 hours, or from 3 hoursto 5 hours.

For the thermal process of preparing the organoaluminum compound of theformula Al(CH₂CH(Y²)A²)₃, Y² and A² may be any of the previouslydescribed embodiments. The optional solvent may be any discussed herein.The starting materials in step (a) may comprise a ratio of the aluminumalkyl of the formula Al(d)₃ to the hydrocarbon of the formulaCH₂═C(Y²)A² of 1:10, or 1:5, or 1:3. The starting materials in step (a)may comprise one or more hydrocarbons of the formula CH₂═C(Y²)A²,wherein: Y² at each occurrence of each hydrocarbon independently ishydrogen or a C₁ to C₃₀ hydrocarbyl group; A² at each of occurrence ofeach hydrocarbon independently is a hydrocarbyl group comprising ahindered double bond; and the starting materials comprise a ratio of thealuminum alkyl of the formula Al(d)₃ to the one or more hydrocarbons ofthe formula CH₂═C(Y²)A² of 1:10, or 1:5, or 1:3. In certain embodiments,Y² may be selected from the group consisting of hydrogen, a methylgroup, and an ethyl group, and A² may be selected from among (AA) to(AZ) and (AZ1) discussed previously. In further embodiments, A² may beselected from the group consisting of (AC), (AF), (AM), (AO), (AP),(AS), and (AZ1). The pendant methyl group of (AF) may be connected toany carbon atom that is a ring member. In this process of preparing theorganoaluminum compound of the formula Al(CH₂CH(Y²)A²)₃, any excesshydrocarbon of the formula CH₂═C(Y²)A² may be removed through the use ofvacuum and optional heating.

Alternatively, the organoaluminum compound of the formulaAl(CH₂CH(Y²)A²)₃ may be prepared a catalytic process comprising: (a)combining starting materials comprising a hydrocarbon of the formulaCH₂═CHA², an aluminum alkyl of the formula Al(Y²)₃, a procatalyst, anoptional co-catalyst, and an optional solvent, and (b) recovering aproduct comprising the organoaluminum compound of the formulaAl(CH₂CH(Y²)A²)₃, wherein step (a) is conducted at a temperature from 1°C. to 50° C., or from 10° C. to 40° C., or from 20° C. to 30° C. for atime of 1 to 50 hours, or from 10 to 40 hours, or from 15 to 25 hours,and wherein: Y² at each occurrence independently is a C₁ to C₃₀hydrocarbyl group; and A² at each occurrence independently is ahydrocarbyl group comprising a hindered double bond.

For the catalytic process of preparing the organoaluminum compound ofthe formula Al(CH₂CH(Y²)A²)₃, Y² will be a C₁ to C₃₀ hydrocarbyl groupwhile A² may be any of the previously described embodiments. Each of theprocatalyst, the optional co-catalyst, and the optional solvent may beany disclosed herein. The starting materials in step (a) may comprise aratio of the aluminum alkyl of the formula Al(Y²)₃ to the hydrocarbon ofthe formula CH₂═CHA² of from 1:10, or 1:5, or 1:3. The startingmaterials in step (a) may comprise one or more hydrocarbons of theformula CH₂═CHA², wherein: A² at each occurrence of each hydrocarbonindependently is a hydrocarbyl group comprising a hindered double bond;and the starting materials comprise a ratio of the aluminum alkyl of theformula Al(Y²)₃ to the one or more hydrocarbons of the formulaCH₂═C(Y²)A² of from 1:10, or 1:5, or 1:3. In certain embodiments, Y² maybe a C₁ to C₁₀ alkyl group, and A² may be selected from among (AA) to(AZ) and (AZ1) discussed previously. In further embodiments, A² may beselected from the group consisting of (AC), (AF), (AM), (AO), (AP),(AS), and (AZ1). The pendant methyl group of (AF) may be connected toany carbon atom that is a ring member.

The (c1) Catalyst Component

In certain embodiments, the (c1) catalyst component comprises aprocatalyst. In these embodiments, the procatalyst becomes an activecatalyst to polymerize unsaturated monomers without a co-catalyst. Infurther embodiments, the (c1) catalyst component comprises a procatalystand a co-catalyst, whereby an active catalyst is formed by thecombination of the procatalyst and the co-catalyst. In theseembodiments, the (c1) active catalyst component may comprise a ratio ofthe procatalyst to the co-catalyst of 1:2, or 1:1.5, or 1:1.2.

Suitable procatalysts include but are not limited to those disclosed inWO 2005/090426, WO 2005/090427, WO 2007/035485, WO 2009/012215, WO2014/105411, WO 2017/173080, U.S. Patent Publication Nos. 2006/0199930,2007/0167578, 2008/0311812, and U.S. Pat. Nos. 7,858,706 B2, 7,355,089B2, 8,058,373 B2, and 8,785,554 B2. With reference to the paragraphsbelow, the term “procatalyst” is interchangeable with the terms“catalyst,” “precatalyst,” “catalyst precursor,” “transition metalcatalyst,” “transition metal catalyst precursor,” “polymerizationcatalyst,” “polymerization catalyst precursor,” “transition metalcomplex,” “transition metal compound,” “metal complex,” “metalcompound,” “complex,” and “metal-ligand complex,” and like terms.

Both heterogeneous and homogeneous catalysts may be employed. Examplesof heterogeneous catalysts include the well known Ziegler-Nattacompositions, especially Group 4 metal halides supported on Group 2metal halides or mixed halides and alkoxides and the well known chromiumor vanadium based catalysts. Preferably, the catalysts for use hereinare homogeneous catalysts comprising a relatively pure organometalliccompound or metal complex, especially compounds or complexes based onmetals selected from Groups 3-10 or the Lanthanide series of thePeriodic Table of the Elements.

Metal complexes for use herein may be selected from Groups 3 to 15 ofthe Periodic Table of the Elements containing one or more delocalized,π-bonded ligands or polyvalent Lewis base ligands. Examples includemetallocene, half-metallocene, constrained geometry, and polyvalentpyridylamine, or other polychelating base complexes. The complexes aregenerically depicted by the formula: MK_(k)X_(x)Z_(z), or a dimerthereof, wherein

M is a metal selected from Groups 3-15, preferably 3-10, more preferably4-10, and most preferably Group 4 of the Periodic Table of the Elements;

K independently at each occurrence is a group containing delocalizedπ-electrons or one or more electron pairs through which K is bound to M,said K group containing up to 50 atoms not counting hydrogen atoms,optionally two or more K groups may be joined together forming a bridgedstructure, and further optionally one or more K groups may be bound toZ, to X or to both Z and X;

X independently at each occurrence is a monovalent, anionic moietyhaving up to 40 non-hydrogen atoms, optionally one or more X groups maybe bonded together thereby forming a divalent or polyvalent anionicgroup, and, further optionally, one or more X groups and one or more Zgroups may be bonded together thereby forming a moiety that is bothcovalently bound to M and coordinated thereto; or two X groups togetherform a divalent anionic ligand group of up to 40 non-hydrogen atoms ortogether are a conjugated diene having from 4 to 30 non-hydrogen atomsbound by means of delocalized π-electrons to M, whereupon M is in the +2formal oxidation state, and

Z independently at each occurrence is a neutral, Lewis base donor ligandof up to 50 non-hydrogen atoms containing at least one unshared electronpair through which Z is coordinated to M;

k is an integer from 0 to 3; x is an integer from 1 to 4; z is a numberfrom 0 to 3; and

the sum, k+x, is equal to the formal oxidation state of M.

Suitable metal complexes include those containing from 1 to 3 π-bondedanionic or neutral ligand groups, which may be cyclic or non-cyclicdelocalized π-bonded anionic ligand groups. Exemplary of such π-bondedgroups are conjugated or nonconjugated, cyclic or non-cyclic diene anddienyl groups, allyl groups, boratabenzene groups, phosphole, and arenegroups. By the term “π-bonded” is meant that the ligand group is bondedto the transition metal by a sharing of electrons from a partiallydelocalized π-bond.

Each atom in the delocalized π-bonded group may independently besubstituted with a radical selected from the group consisting ofhydrogen, halogen, hydrocarbyl, halohydrocarbyl, hydrocarbyl-substitutedheteroatoms wherein the heteroatom is selected from Group 14-16 of thePeriodic Table of the Elements, and such hydrocarbyl-substitutedheteroatom radicals further substituted with a Group 15 or 16 heteroatom containing moiety. In addition, two or more such radicals maytogether form a fused ring system, including partially or fullyhydrogenated fused ring systems, or they may form a metallocycle withthe metal. Included within the term “hydrocarbyl” are C₁₋₂₀ straight,branched and cyclic alkyl radicals, C₆-20 aromatic radicals, C₇-20alkyl-substituted aromatic radicals, and C₇-20 aryl-substituted alkylradicals. Suitable hydrocarbyl-substituted heteroatom radicals includemono-, di- and tri-substituted radicals of boron, silicon, germanium,nitrogen, phosphorus or oxygen wherein each of the hydrocarbyl groupscontains from 1 to 20 carbon atoms. Examples include N,N-dimethylamino,pyrrolidinyl, trimethylsilyl, triethylsilyl, t-butyldimethylsilyl,methyldi(t-butyl)silyl, triphenylgermyl, and trimethylgermyl groups.Examples of Group 15 or 16 hetero atom containing moieties includeamino, phosphino, alkoxy, or alkylthio moieties or divalent derivativesthereof, for example, amide, phosphide, alkyleneoxy or alkylenethiogroups bonded to the transition metal or Lanthanide metal, and bonded tothe hydrocarbyl group, π-bonded group, or hydrocarbyl-substitutedheteroatom.

Examples of suitable anionic, delocalized π-bonded groups includecyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl,tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl,dihydroanthracenyl, hexahydroanthracenyl, decahydroanthracenyl groups,phosphole, and boratabenzyl groups, as well as inertly substitutedderivatives thereof, especially C₁₋₁₀ hydrocarbyl-substituted ortris(C₁-10 hydrocarbyl)silyl-substituted derivatives thereof. Preferredanionic delocalized π-bonded groups are cyclopentadienyl,pentamethylcyclopentadienyl, tetramethylcyclopentadienyl,tetramethylsilylcyclopentadienyl, indenyl, 2,3-dimethylindenyl,fluorenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl,tetrahydrofluorenyl, octahydrofluorenyl, 1-indacenyl,3-pyrrolidinoinden-1-yl, 3,4-(cyclopenta(1)phenanthren-1-yl, andtetrahydroindenyl.

The boratabenzenyl ligands are anionic ligands which are boroncontaining analogues to benzene. They are previously known in the arthaving been described by G. Herberich, et al., in Organometallics, 14,1, 471-480 (1995). Preferred boratabenzenyl ligands correspond to theformula:

wherein R¹ is an inert substituent, preferably selected from the groupconsisting of hydrogen, hydrocarbyl, silyl, halo or germyl, said R¹having up to 20 atoms not counting hydrogen, and optionally two adjacentR¹ groups may be joined together. In complexes involving divalentderivatives of such delocalized π-bonded groups one atom thereof isbonded by means of a covalent bond or a covalently bonded divalent groupto another atom of the complex thereby forming a bridged system.

Phospholes are anionic ligands that are phosphorus containing analoguesto a cyclopentadienyl group. They are previously known in the art havingbeen described by WO 98/50392, and elsewhere. Preferred phospholeligands correspond to the formula:

wherein R¹ is as previously defined.

Suitable transition metal complexes for use herein correspond to theformula: MK_(k)X_(x)Z_(z), or a dimer thereof, wherein:

M is a Group 4 metal;

K is a group containing delocalized π-electrons through which K is boundto M, said K group containing up to 50 atoms not counting hydrogenatoms, optionally two K groups may be joined together forming a bridgedstructure, and further optionally one K may be bound to X or Z;

X at each occurrence is a monovalent, anionic moiety having up to 40non-hydrogen atoms, optionally one or more X and one or more K groupsare bonded together to form a metallocycle, and further optionally oneor more X and one or more Z groups are bonded together thereby forming amoiety that is both covalently bound to M and coordinated thereto;

Z independently at each occurrence is a neutral, Lewis base donor ligandof up to 50 non-hydrogen atoms containing at least one unshared electronpair through which Z is coordinated to M;

-   -   k is an integer from 0 to 3; x is an integer from 1 to 4; z is a        number from 0 to 3; and the sum, k+x, is equal to the formal        oxidation state of M.

Suitable complexes include those containing either one or two K groups.The latter complexes include those containing a bridging group linkingthe two K groups. Suitable bridging groups are those corresponding tothe formula (ER′₂)_(e) wherein E is silicon, germanium, tin, or carbon,R′ independently at each occurrence is hydrogen or a group selected fromsilyl, hydrocarbyl, hydrocarbyloxy and combinations thereof, said R′having up to 30 carbon or silicon atoms, and e is 1 to 8.Illustratively, R′ independently at each occurrence is methyl, ethyl,propyl, benzyl, tert-butyl, phenyl, methoxy, ethoxy or phenoxy.

Examples of the complexes containing two K groups are compoundscorresponding to the formula:

wherein:

M is titanium, zirconium or hafnium, preferably zirconium or hafnium, inthe +2 or +4 formal oxidation state; R³ at each occurrence independentlyis selected from the group consisting of hydrogen, hydrocarbyl, silyl,germyl, cyano, halo and combinations thereof, said R³ having up to 20non-hydrogen atoms, or adjacent R³ groups together form a divalentderivative (that is, a hydrocarbadiyl, siladiyl or germadiyl group)thereby forming a fused ring system, and

X″ independently at each occurrence is an anionic ligand group of up to40 non-hydrogen atoms, or two X″ groups together form a divalent anionicligand group of up to 40 non-hydrogen atoms or together are a conjugateddiene having from 4 to 30 non-hydrogen atoms bound by means ofdelocalized π-electrons to M, whereupon M is in the +2 formal oxidationstate, and R′, E and e are as previously defined.

Exemplary bridged ligands containing two π-bonded groups are:dimethylbis(cyclopentadienyl)silane,dimethylbis(tetramethylcyclopentadienyl)silane,dimethylbis(2-ethylcyclopentadien-1-yl)silane,dimethylbis(2-t-butylcyclopentadien-1-yl)silane,2,2-bis(tetramethylcyclopentadienyl)propane,dimethylbis(inden-1-yl)silane, dimethylbis(tetrahydroinden-1-yl)silane,dimethylbis(fluoren-1-yl)silane,dimethylbis(tetrahydrofluoren-1-yl)silane,dimethylbis(2-methyl-4-phenylinden-1-yl)-silane,dimethylbis(2-methylinden-1-yl)silane,dimethyl(cyclopentadienyl)(fluoren-1-yl)silane,dimethyl(cyclopentadienyl)(octahydrofluoren-1-yl)silane,dimethyl(cyclopentadienyl)(tetrahydrofluoren-1-yl)silane,(1,1,2,2-tetramethy)-1,2-bis(cyclopentadienyl)disilane,(1,2-bis(cyclopentadienyl)ethane, anddimethyl(cyclopentadienyl)-1-(fluoren-1-yl)methane.

Suitable X″ groups are selected from hydride, hydrocarbyl, silyl,germyl, halohydrocarbyl, halosilyl, silylhydrocarbyl andaminohydrocarbyl groups, or two X″ groups together form a divalentderivative of a conjugated diene or else together they form a neutral,π-bonded, conjugated diene. Exemplary X″ groups are C1-20 hydrocarbylgroups.

A further class of metal complexes utilized in the present disclosurecorresponds to the preceding formula: MKZ_(z)X_(x), or a dimer thereof,wherein M, K, X, x and z are as previously defined, and Z is asubstituent of up to 50 non-hydrogen atoms that together with K forms ametallocycle with M.

Suitable Z substituents include groups containing up to 30 non-hydrogenatoms comprising at least one atom that is oxygen, sulfur, boron or amember of Group 14 of the Periodic Table of the Elements directlyattached to K, and a different atom, selected from the group consistingof nitrogen, phosphorus, oxygen or sulfur that is covalently bonded toM.

More specifically this class of Group 4 metal complexes used accordingto the present invention includes “constrained geometry catalysts”corresponding to the formula:

wherein: M is titanium or zirconium, preferably titanium in the +2, +3,or +4 formal oxidation state;

K¹ is a delocalized, n-bonded ligand group optionally substituted withfrom 1 to 5 R² groups,

R² at each occurrence independently is selected from the groupconsisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo andcombinations thereof, said R² having up to 20 non-hydrogen atoms, oradjacent R² groups together form a divalent derivative (that is, ahydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fusedring system,

each X is a halo, hydrocarbyl, heterohydrocarbyl, hydrocarbyloxy orsilyl group, said group having up to 20 non-hydrogen atoms, or two Xgroups together form a neutral C5-30 conjugated diene or a divalentderivative thereof;

x is 1 or 2;

Y is —O—, —S—, —NR′—, —PR′—;

and X′ is SiR′₂, CR′₂, SiR′₂SiR′₂, CR′₂CR′₂, CR′═CR′, CR′₂SiR′₂, orGeR′₂, wherein R′ independently at each occurrence is hydrogen or agroup selected from silyl, hydrocarbyl, hydrocarbyloxy and combinationsthereof, said R′ having up to 30 carbon or silicon atoms.

Specific examples of the foregoing constrained geometry metal complexesinclude compounds corresponding to the formula:

wherein,

Ar is an aryl group of from 6 to 30 atoms not counting hydrogen;

R⁴ independently at each occurrence is hydrogen, Ar, or a group otherthan Ar selected from hydrocarbyl, trihydrocarbylsilyl,trihydrocarbylgermyl, halide, hydrocarbyloxy, trihydrocarbylsiloxy,bis(trihydrocarbylsilyl)amino, di(hydrocarbyl)amino,hydrocarbadiylamino, hydrocarbylimino, di(hydrocarbyl)phosphino,hydrocarbadiylphosphino, hydrocarbylsulfido, halo-substitutedhydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl,trihydrocarbylsilyl-substituted hydrocarbyl,trihydrocarbylsiloxy-substituted hydrocarbyl,bis(trihydrocarbylsilyl)amino-substituted hydrocarbyl,di(hydrocarbyl)amino-substituted hydrocarbyl,hydrocarbyleneamino-substituted hydrocarbyl,di(hydrocarbyl)phosphino-substituted hydrocarbyl,hydrocarbylenephosphino-substituted hydrocarbyl, orhydrocarbylsulfido-substituted hydrocarbyl, said R group having up to 40atoms not counting hydrogen atoms, and optionally two adjacent R⁴ groupsmay be joined together forming a polycyclic fused ring group;

M is titanium;

X′ is SiR⁶ ₂, CR⁶ ₂, SiR⁶ ₂SiR⁶ ₂, CR⁶ ₂CR⁶ ₂, CR⁶═CR⁶, CR⁶ ₂SiR⁶ ₂,BR⁶, BR⁶L″, or GeR⁶ ₂;

Y is —O—, —S—, —NR—, —PR—; —NR⁵ ₂, or —PR⁵ ₂;

R⁵, independently at each occurrence is hydrocarbyl,trihydrocarbylsilyl, or trihydrocarbylsilylhydrocarbyl, said R⁵ havingup to 20 atoms other than hydrogen, and optionally two R⁵ groups or R⁵together with Y or Z form a ring system;

R⁶, independently at each occurrence, is hydrogen, or a member selectedfrom hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenatedaryl, —NR⁵ ₂, and combinations thereof, said R⁶ having up to 20non-hydrogen atoms, and optionally, two R⁶ groups or R⁶ together with Zforms a ring system;

Z is a neutral diene or a monodentate or polydentate Lewis baseoptionally bonded to R⁵, R⁶, or X;

X is hydrogen, a monovalent anionic ligand group having up to 60 atomsnot counting hydrogen, or two X groups are joined together therebyforming a divalent ligand group;

x is 1 or 2; and

z is 0, 1 or 2.

Additional examples of suitable metal complexes herein are polycycliccomplexes corresponding to the formula:

where M is titanium in the +2, +3 or +4 formal oxidation state;

R⁷ independently at each occurrence is hydride, hydrocarbyl, silyl,germyl, halide, hydrocarbyloxy, hydrocarbylsiloxy,hydrocarbylsilylamino, di(hydrocarbyl)amino, hydrocarbyleneamino,di(hydrocarbyl)phosphino, hydrocarbylene-phosphino, hydrocarbylsulfido,halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl,silyl-substituted hydrocarbyl, hydrocarbylsiloxy-substitutedhydrocarbyl, hydrocarbylsilylamino-substituted hydrocarbyl,di(hydrocarbyl)amino-substituted hydrocarbyl,hydrocarbyleneamino-substituted hydrocarbyl,di(hydrocarbyl)phosphino-substituted hydrocarbyl,hydrocarbylene-phosphino-substituted hydrocarbyl, orhydrocarbylsulfido-substituted hydrocarbyl, said R⁷ group having up to40 atoms not counting hydrogen, and optionally two or more of theforegoing groups may together form a divalent derivative;

R⁸ is a divalent hydrocarbylene- or substituted hydrocarbylene groupforming a fused system with the remainder of the metal complex, said R⁸containing from 1 to 30 atoms not counting hydrogen;

X^(a) is a divalent moiety, or a moiety comprising one π-bond and aneutral two electron pair able to form a coordinate-covalent bond to M,said X^(a) comprising boron, or a member of Group 14 of the PeriodicTable of the Elements, and also comprising nitrogen, phosphorus, sulfuror oxygen;

X is a monovalent anionic ligand group having up to 60 atoms exclusiveof the class of ligands that are cyclic, delocalized, π-bound ligandgroups and optionally two X groups together form a divalent ligandgroup;

Z independently at each occurrence is a neutral ligating compound havingup to 20 atoms;

x is 0, 1 or 2; and

z is zero or 1.

Additional examples of metal complexes that are usefully employed ascatalysts are complexes of polyvalent Lewis bases, such as compoundscorresponding to the formula:

wherein T^(b) is a bridging group, preferably containing 2 or more atomsother than hydrogen,

X^(b) and Y^(b) are each independently selected from the groupconsisting of nitrogen, sulfur, oxygen and phosphorus; more preferablyboth X^(b) and Y^(b) are nitrogen,

R^(b) and R^(b)′ independently each occurrence are hydrogen or C₁₋₅₀hydrocarbyl groups optionally containing one or more heteroatoms orinertly substituted derivative thereof. Non-limiting examples ofsuitable R^(b) and R^(b)′ groups include alkyl, alkenyl, aryl, aralkyl,(poly)alkylaryl and cycloalkyl groups, as well as nitrogen, phosphorus,oxygen and halogen substituted derivatives thereof. Specific examples ofsuitable R^(b) and R^(b′) groups include methyl, ethyl, isopropyl,octyl, phenyl, 2,6-dimethylphenyl, 2,6-di(isopropyl)phenyl,2,4,6-trimethylphenyl, pentafluorophenyl, 3,5-trifluoromethylphenyl, andbenzyl;

g and g′ are each independently 0 or 1;

M^(b) is a metallic element selected from Groups 3 to 15, or theLanthanide series of the Periodic Table of the Elements. Preferably,M^(b) is a Group 3-13 metal, more preferably M^(b) is a Group 4-10metal;

L^(b) is a monovalent, divalent, or trivalent anionic ligand containingfrom 1 to 50 atoms, not counting hydrogen. Examples of suitable L^(b)groups include halide; hydride; hydrocarbyl, hydrocarbyloxy;di(hydrocarbyl)amido, hydrocarbyleneamido, di(hydrocarbyl)phosphido;hydrocarbylsulfido; hydrocarbyloxy, tri(hydrocarbylsilyl)alkyl; andcarboxylates. More preferred L^(b) groups are C₁-20 alkyl, C₇-20aralkyl, and chloride;

h and h′ are each independently an integer from 1 to 6, preferably from1 to 4, more preferably from 1 to 3, and j is 1 or 2, with the value h xj selected to provide charge balance;

Z^(b) is a neutral ligand group coordinated to M^(b), and containing upto 50 atoms not counting hydrogen. Preferred Z^(b) groups includealiphatic and aromatic amines, phosphines, and ethers, alkenes,alkadienes, and inertly substituted derivatives thereof. Suitable inertsubstituents include halogen, alkoxy, aryloxy, alkoxycarbonyl,aryloxycarbonyl, di(hydrocarbyl)amine, tri(hydrocarbyl)silyl, andnitrile groups. Preferred Z^(b) groups include triphenylphosphine,tetrahydrofuran, pyridine, and 1,4-diphenylbutadiene;

f is an integer from 1 to 3;

two or three of T^(b), R^(b) and R^(b)′ may be joined together to form asingle or multiple ring structure;

h is an integer from 1 to 6, preferably from 1 to 4, more preferablyfrom 1 to 3;

In one embodiment, it is preferred that R^(b) have relatively low sterichindrance with respect to X^(b). In this embodiment, most preferredR^(b) groups are straight chain alkyl groups, straight chain alkenylgroups, branched chain alkyl groups wherein the closest branching pointis at least 3 atoms removed from X^(b), and halo, dihydrocarbylamino,alkoxy or trihydrocarbylsilyl substituted derivatives thereof. Highlypreferred R^(b) groups in this embodiment are C1-8 straight chain alkylgroups.

At the same time, in this embodiment R^(b)′ preferably has relativelyhigh steric hindrance with respect to Y^(b). Non-limiting examples ofsuitable R^(b)′ groups for this embodiment include alkyl or alkenylgroups containing one or more secondary or tertiary carbon centers,cycloalkyl, aryl, alkaryl, aliphatic or aromatic heterocyclic groups,organic or inorganic oligomeric, polymeric or cyclic groups, and halo,dihydrocarbylamino, alkoxy or trihydrocarbylsilyl substitutedderivatives thereof. Preferred R^(b)′ groups in this embodiment containfrom 3 to 40, more preferably from 3 to 30, and most preferably from 4to 20 atoms not counting hydrogen and are branched or cyclic. Examplesof preferred T^(b) groups are structures corresponding to the followingformulas:

wherein

Each R^(d) is C1-10 hydrocarbyl group, preferably methyl, ethyl,n-propyl, i-propyl, t-butyl, phenyl, 2,6-dimethylphenyl, benzyl, ortolyl. Each R^(e) is C1-10 hydrocarbyl, preferably methyl, ethyl,n-propyl, i-propyl, t-butyl, phenyl, 2,6-dimethylphenyl, benzyl, ortolyl. In addition, two or more R^(d) or R^(e) groups, or mixtures of Rdand Re groups may together form a divalent or polyvalent derivative of ahydrocarbyl group, such as, 1,4-butylene, 1,5-pentylene, or a cyclicring, or a multicyclic fused ring, polyvalent hydrocarbyl- orheterohydrocarbyl-group, such as naphthalene-1,8-diyl.

Suitable examples of the foregoing polyvalent Lewis base complexesinclude:

wherein R^(d′) at each occurrence is independently selected from thegroup consisting of hydrogen and C₁-50 hydrocarbyl groups optionallycontaining one or more heteroatoms, or inertly substituted derivativethereof, or further optionally, two adjacent R^(d′) groups may togetherform a divalent bridging group;

d′ is 4;

M^(b′) is a Group 4 metal, preferably titanium or hafnium, or a Group 10metal, preferably Ni or Pd;

L^(b′) is a monovalent ligand of up to 50 atoms not counting hydrogen,preferably halide or hydrocarbyl, or two L^(b′) groups together are adivalent or neutral ligand group, preferably a C₂₋₅₀ hydrocarbylene,hydrocarbadiyl or diene group.

The polyvalent Lewis base complexes for use in the present inventionespecially include Group 4 metal derivatives, especially hafniumderivatives of hydrocarbylamine substituted heteroaryl compoundscorresponding to the formula:

wherein:

R¹¹ is selected from alkyl, cycloalkyl, heteroalkyl, cycloheteroalkyl,aryl, and inertly substituted derivatives thereof containing from 1 to30 atoms not counting hydrogen or a divalent derivative thereof;

T¹ is a divalent bridging group of from 1 to 41 atoms other thanhydrogen, preferably 1 to 20 atoms other than hydrogen, and mostpreferably a mono- or di-C₁-20 hydrocarbyl substituted methylene orsilane group; and

R¹² is a C₅-20 heteroaryl group containing Lewis base functionality,especially a pyridin-2-yl- or substituted pyridin-2-yl group or adivalent derivative thereof;

M¹ is a Group 4 metal, preferably hafnium;

X¹ is an anionic, neutral or dianionic ligand group;

x′ is a number from 0 to 5 indicating the number of such X¹ groups; andbonds, optional bonds and electron donative interactions are representedby lines, dotted lines and arrows respectively.

Suitable complexes are those wherein ligand formation results fromhydrogen elimination from the amine group and optionally from the lossof one or more additional groups, especially from R¹². In addition,electron donation from the Lewis base functionality, preferably anelectron pair, provides additional stability to the metal center.Suitable metal complexes correspond to the formula:

wherein M¹, X¹, x′, R11 and T¹ and are as previously defined,R¹³, R¹⁴, R¹⁵ and R₁₆ are hydrogen, halo, or an alkyl, cycloalkyl,heteroalkyl, heterocycloalkyl, aryl, or silyl group of up to 20 atomsnot counting hydrogen, or adjacent R¹³, R¹⁴, R¹⁵ or R¹⁶ groups may bejoined together thereby forming fused ring derivatives, and bonds,optional bonds and electron pair donative interactions are representedby lines, dotted lines and arrows respectively. Suitable examples of theforegoing metal complexes correspond to the formula:

whereinM¹, X¹, x′ and are as previously defined,R¹³, R¹⁴, R¹⁵ and R¹⁶ are as previously defined, preferably R¹³, R¹⁴,and R¹⁵ are hydrogen, or C1-4 alkyl, and R¹⁶ is C₆₋₂₀ aryl, mostpreferably naphthalenyl;R^(a) independently at each occurrence is C₁-4 alkyl, and a is 1-5, mostpreferably R^(a) in two ortho-positions to the nitrogen is isopropyl ort-butyl;R¹⁷ and R¹⁸ independently at each occurrence are hydrogen, halogen, or aC₁₋₂₀ alkyl or aryl group, most preferably one of R¹⁷ and R¹⁸ ishydrogen and the other is a C6-20 aryl group, especially 2-isopropyl,phenyl or a fused polycyclic aryl group, most preferably an anthracenylgroup, and bonds, optional bonds and electron pair donative interactionsare represented by lines, dotted lines and arrows respectively.

Exemplary metal complexes for use herein as catalysts correspond to theformula:

wherein X¹ at each occurrence is halide, N,N-dimethylamido, or C₁-4alkyl, and preferably at each occurrence X¹ is methyl;R^(f) independently at each occurrence is hydrogen, halogen, C1-20alkyl, or C6-20 aryl, or two adjacent R^(f) groups are joined togetherthereby forming a ring, and f is 1-5; andR^(c) independently at each occurrence is hydrogen, halogen, C₁₋₂₀alkyl, or C₆₋₂₀ aryl, or two adjacent R^(c) groups are joined togetherthereby forming a ring, and c is 1-5.

Suitable examples of metal complexes for use as catalysts according tothe present invention are complexes of the following formulas:

wherein R^(x) is C1-4 alkyl or cycloalkyl, preferably methyl, isopropyl,t-butyl or cyclohexyl; and X¹ at each occurrence is halide,N,N-dimethylamido, or C1-4 alkyl, preferably methyl.

Examples of metal complexes usefully employed as catalysts according tothe present invention include:

-   [N-(2,6-di(1-methylethyl)phenyl)amido)(o-tolyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium    dimethyl;-   [N-(2,6-di(1-methylethyl)phenyl)amido)(o-tolyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium    di(N,N-dimethylamido);-   [N-(2,6-di(1-methylethyl)phenyl)amido)(o-tolyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium    dichloride;-   [N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium    dimethyl;-   [N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium    di(N,N-dimethylamido);-   [N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium    dichloride;-   [N-(2,6-di(1-methylethyl)phenyl)amido)(phenanthren-5-yl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium    dimethyl;-   [N-(2,6-di(1-methylethyl)phenyl)amido)(phenanthren-5-yl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium    di(N,N-dimethylamido); and-   [N-(2,6-di(1-methylethyl)phenyl)amido)(phenanthren-5-yl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium    dichloride.

Under the reaction conditions used to prepare the metal complexes usedin the present disclosure, the hydrogen of the 2-position of theα-naphthalene group substituted at the 6-position of the pyridin-2-ylgroup is subject to elimination, thereby uniquely forming metalcomplexes wherein the metal is covalently bonded to both the resultingamide group and to the 2-position of the α-naphthalenyl group, as wellas stabilized by coordination to the pyridinyl nitrogen atom through theelectron pair of the nitrogen atom.

Further procatalysts that are suitable include imidazole-amine compoundscorresponding to those disclosed in WO 2007/130307A2, WO 2007/130306A2,and U.S. Patent Application Publication No. 20090306318A1, which areincorporated herein by reference in their entirety. Such imidazole-aminecompounds include those corresponding to the formula:

wherein

X independently each occurrence is an anionic ligand, or two X groupstogether form a dianionic ligand group, or a neutral diene; T is acycloaliphatic or aromatic group containing one or more rings; R¹independently each occurrence is hydrogen, halogen, or a univalent,polyatomic anionic ligand, or two or more R¹ groups are joined togetherthereby forming a polyvalent fused ring system; R² independently eachoccurrence is hydrogen, halogen, or a univalent, polyatomic anionicligand, or two or more R² groups are joined together thereby forming apolyvalent fused ring system; and R⁴ is hydrogen, alkyl, aryl, aralkyl,trihydrocarbylsilyl, or trihydrocarbylsilylmethyl of from 1 to 20carbons.

Further examples of such imidazole-amine compounds include but are notlimited to the following:

wherein:

R¹ independently each occurrence is a C₃₋₁₂ alkyl group wherein thecarbon attached to the phenyl ring is secondary or tertiary substituted;R² independently each occurrence is hydrogen or a C₁₋₂ alkyl group; R⁴is methyl or isopropyl; R⁵ is hydrogen or C₁₋₆alkyl; R⁶ is hydrogen,C₁₋₆ alkyl or cycloalkyl, or two adjacent R⁶ groups together form afused aromatic ring; T′ is oxygen, sulfur, or a C₁₋₂₀hydrocarbyl-substituted nitrogen or phosphorus group; T″ is nitrogen orphosphorus; and X is methyl or benzyl.

Additional suitable metal complexes of polyvalent Lewis bases for useherein include compounds corresponding to the formula:

wherein:R²⁰ is an aromatic or inertly substituted aromatic group containing from5 to 20 atoms not counting hydrogen, or a polyvalent derivative thereof;T³ is a hydrocarbylene or hydrocarbyl silane group having from 1 to 20atoms not counting hydrogen, or an inertly substituted derivativethereof;M³ is a Group 4 metal, preferably zirconium or hafnium;G is an anionic, neutral or dianionic ligand group; preferably a halide,hydrocarbyl, silane, trihydrocarbylsilylhydrocarbyl,trihydrocarbylsilyl, or dihydrocarbylamide group having up to 20 atomsnot counting hydrogen;g is a number from 1 to 5 indicating the number of such G groups; andbonds and electron donative interactions are represented by lines andarrows respectively.

Illustratively, such complexes correspond to the formula:

wherein:T³ is a divalent bridging group of from 2 to 20 atoms not countinghydrogen, preferably a substituted or unsubstituted, C3-6 alkylenegroup;and Ar² independently at each occurrence is an arylene or an alkyl- oraryl-substituted arylene group of from 6 to 20 atoms not countinghydrogen;M³ is a Group 4 metal, preferably hafnium or zirconium;G independently at each occurrence is an anionic, neutral or dianionicligand group;g is a number from 1 to 5 indicating the number of such X groups; andelectron donative interactions are represented by arrows.

Suitable examples of metal complexes of foregoing formula include thefollowing compounds

where M³ is Hf or Zr;

Ar⁴ is C₆₋₂₀ aryl or inertly substituted derivatives thereof, especially3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl,dibenzo-1H-pyrrole-1-yl, or anthracen-5-yl, and

T⁴ independently at each occurrence comprises a C₃₋₆ alkylene group, aC₃₋₆ cycloalkylene group, or an inertly substituted derivative thereof;

R²¹ independently at each occurrence is hydrogen, halo, hydrocarbyl,trihydrocarbylsilyl, or trihydrocarbylsilylhydrocarbyl of up to 50 atomsnot counting hydrogen; and

G, independently at each occurrence is halo or a hydrocarbyl ortrihydrocarbylsilyl group of up to 20 atoms not counting hydrogen, or 2G groups together are a divalent derivative of the foregoing hydrocarbylor trihydrocarbylsilyl groups.

Suitable compounds are compounds of the formulas:

wherein Ar⁴ is 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl,dibenzo-1H-pyrrole-1-yl, or anthracen-5-yl,

R²¹ is hydrogen, halo, or C1-4 alkyl, especially methyl

T⁴ is propan-1,3-diyl or butan-1,4-diyl, and

G is chloro, methyl or benzyl.

Exemplary metal complexes of the foregoing formula are:

Suitable metal complexes for use according to the present disclosurefurther include compounds corresponding to the formula:

where:M is zirconium or hafnium;R²⁰ independently at each occurrence is a divalent aromatic or inertlysubstituted aromatic group containing from 5 to 20 atoms not countinghydrogen;T³ is a divalent hydrocarbon or silane group having from 3 to 20 atomsnot counting hydrogen, or an inertly substituted derivative thereof; andR^(D) independently at each occurrence is a monovalent ligand group offrom 1 to 20 atoms, not counting hydrogen, or two R^(D) groups togetherare a divalent ligand group of from 1 to 20 atoms, not countinghydrogen.

Such complexes may correspond to the formula:

wherein:Ar² independently at each occurrence is an arylene or an alkyl-, aryl-,alkoxy- or amino-substituted arylene group of from 6 to 20 atoms notcounting hydrogen or any atoms of any substituent;T³ is a divalent hydrocarbon bridging group of from 3 to 20 atoms notcounting hydrogen, preferably a divalent substituted or unsubstitutedC₃₋₆ aliphatic, cycloaliphatic, or bis(alkylene)-substitutedcycloaliphatic group having at least 3 carbon atoms separating oxygenatoms; andR^(D) independently at each occurrence is a monovalent ligand group offrom 1 to 20 atoms, not counting hydrogen, or two R^(D) groups togetherare a divalent ligand group of from 1 to 40 atoms, not countinghydrogen.

Further examples of metal complexes suitable for use herein includecompounds of the formula:

whereAr⁴ independently at each occurrence is C₆₋₂₀ aryl or inertlysubstituted derivatives thereof, especially 3,5-di(isopropyl)phenyl,3,5-di(isobutyl)phenyl, dibenzo-1H-pyrrole-1-yl, naphthyl,anthracen-5-yl, 1,2,3,4,6,7,8,9-octahydroanthracen-5-yl;T⁴ independently at each occurrence is a propylene-1,3-diyl group, abis(alkylene)cyclohexan-1,2-diyl group, or an inertly substitutedderivative thereof substituted with from 1 to 5 alkyl, aryl or aralkylsubstituents having up to 20 carbons each;R²¹ independently at each occurrence is hydrogen, halo, hydrocarbyl,trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or amino ofup to 50 atoms not counting hydrogen; andR^(D), independently at each occurrence is halo or a hydrocarbyl ortrihydrocarbylsilyl group of up to 20 atoms not counting hydrogen, or 2R^(D) groups together are a divalent hydrocarbylene, hydrocarbadiyl ortrihydrocarbylsilyl group of up to 40 atoms not counting hydrogen.

Exemplary metal complexes are compounds of the formula:

where, Ar⁴, independently at each occurrence, is3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl,dibenzo-1H-pyrrole-1-yl, or anthracen-5-yl,R²¹ independently at each occurrence is hydrogen, halo, hydrocarbyl,trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy or amino ofup to 50 atoms not counting hydrogen;T⁴ is propan-1,3-diyl or bis(methylene)cyclohexan-1,2-diyl; andR^(D), independently at each occurrence is halo or a hydrocarbyl ortrihydrocarbylsilyl group of up to 20 atoms not counting hydrogen, or 2R^(D) groups together are a hydrocarbylene, hydrocarbadiyl orhydrocarbylsilanediyl group of up to 40 atoms not counting hydrogen.

Suitable metal complexes according to the present disclosure correspondto the formulas:

wherein, R^(D) independently at each occurrence is chloro, methyl orbenzyl.

Specific examples of suitable metal complexes are the followingcompounds:

-   A)    bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium (IV)    dimethyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium (IV)    dichloride,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium (IV)    dibenzyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium (IV)    dimethyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium (IV)    dichloride,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium (IV)    dibenzyl,-   B)    bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium (IV)    dimethyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium (IV)    dichloride,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium (IV)    dibenzyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium (IV)    dimethyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium (IV)    dichloride,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium (IV)    dibenzyl,-   C)    bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium (IV)    dimethyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium (IV)    dichloride,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium (IV)    dibenzyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium (IV)    dimethyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium (IV)    dichloride,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium (IV)    dibenzyl,-   D)    bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediylhafnium (IV)    dimethyl,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediylhafnium (IV)    dichloride,-   bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediylhafnium (IV)    dibenzyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediylhafnium (IV)    dimethyl,-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediylhafnium (IV)    dichloride, and-   bis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylenetrans-1,2-cyclohexanediylhafnium (IV)    dibenzyl.

The foregoing metal complexes may be conveniently prepared by standardmetallation and ligand exchange procedures involving a source of thetransition metal and a neutral polyfunctional ligand source. Thetechniques employed are the same as or analogous to those disclosed inU.S. Pat. No. 6,827,976 and US2004/0010103, and elsewhere.

The foregoing polyvalent Lewis base complexes are conveniently preparedby standard metallation and ligand exchange procedures involving asource of the Group 4 metal and the neutral polyfunctional ligandsource. In addition, the complexes may also be prepared by means of anamide elimination and hydrocarbylation process starting from thecorresponding Group 4 metal tetraamide and a hydrocarbylating agent,such as trimethylaluminum. Other techniques may be used as well. Thesecomplexes are known from the disclosures of, among others, U.S. Pat.Nos. 6,320,005, 6,103,657, WO 02/38628, WO 03/40195, and U.S. Ser. No.04/022,0050.

Catalysts having high comonomer incorporation properties are also knownto reincorporate in situ prepared long chain olefins resultingincidentally during the polymerization through β-hydride elimination andchain termination of growing polymer, or other process. Theconcentration of such long chain olefins is particularly enhanced by useof continuous solution polymerization conditions at high conversions,especially ethylene conversions of 95 percent or greater, morepreferably at ethylene conversions of 97 percent or greater. Under suchconditions a small but detectable quantity of olefin terminated polymermay be reincorporated into a growing polymer chain, resulting in theformation of long chain branches, that is, branches of a carbon lengthgreater than would result from other deliberately added comonomer.Moreover, such chains reflect the presence of other comonomers presentin the reaction mixture. That is, the chains may include short chain orlong chain branching as well, depending on the comonomer composition ofthe reaction mixture. Long chain branching of olefin polymers is furtherdescribed in U.S. Pat. Nos. 5,272,236, 5,278,272, and 5,665,800.

Alternatively, branching, including hyper-branching, may be induced in aparticular segment of the present multi-block copolymers by the use ofspecific catalysts known to result in “chain-walking” in the resultingpolymer. For example, certain homogeneous bridged bis indenyl- orpartially hydrogenated bis indenyl-zirconium catalysts, disclosed byKaminski, et al., J. Mol. Catal. A: Chemical, 102 (1995) 59-65;Zambelli, et al., Macromolecules, 1988, 21, 617-622; or Dias, et al., J.Mol. Catal. A: Chemical, 185 (2002) 57-64 may be used to preparebranched copolymers from single monomers, including ethylene.

Additional complexes suitable for use include Group 4-10 derivativescorresponding to the formula:

whereinM² is a metal of Groups 4-10 of the Periodic Table of the elements,preferably Group 4 metals, Ni(II) or POT), most preferably zirconium;

-   T² is a nitrogen, oxygen or phosphorus containing group;    X² is halo, hydrocarbyl, or hydrocarbyloxy;    t is one or two;    x″ is a number selected to provide charge balance;    and T² and N are linked by a bridging ligand.

Such catalysts have been previously disclosed in J. Am. Chem. Soc., 118,267-268 (1996), J. Am. Chem. Soc., 117, 6414-6415 (1995), andOrganometallics, 16, 1514-1516, (1997), among other disclosures.

Suitable examples of the foregoing metal complexes for use as catalystsare aromatic diimine or aromatic dioxyimine complexes of Group 4 metals,especially zirconium, corresponding to the formula:

wherein;M², X² and T² are as previously defined;R^(d) independently in each occurrence is hydrogen, halogen, or R^(e);andR^(e) independently in each occurrence is C1-20 hydrocarbyl or aheteroatom-, especially a F, N, S or P-substituted derivative thereof,more preferably C1-20 hydrocarbyl or a F or N substituted derivativethereof, most preferably alkyl, dialkylaminoalkyl, pyrrolyl,piperidenyl, perfluorophenyl, cycloalkyl, (poly)alkylaryl, or aralkyl.

Suitable examples of the foregoing metal complexes for use as catalystsare aromatic dioxyimine complexes of zirconium, corresponding to theformula:

wherein;X² is as previously defined, preferably C1-10 hydrocarbyl, mostpreferably methyl or benzyl; andR^(e′) is methyl, isopropyl, t-butyl, cyclopentyl, cyclohexyl,2-methylcyclohexyl, 2,4-dimethylcyclohexyl, 2-pyrrolyl,N-methyl-2-pyrrolyl, 2-piperidenyl, N-methyl-2-piperidenyl, benzyl,o-tolyl, 2,6-dimethylphenyl, perfluorophenyl, 2,6-di(isopropyl)phenyl,or 2,4,6-trimethylphenyl.

The foregoing complexes for use as also include certain phosphiniminecomplexes are disclosed in EP-A-890581. These complexes correspond tothe formula: [(R^(f))₃—P═N]_(f)M(K²)(R^(f))_(3-f), wherein: R^(f) is amonovalent ligand or two R¹ groups together are a divalent ligand,preferably R^(f) is hydrogen or C1-4 alkyl;

M is a Group 4 metal,K² is a group containing delocalized π-electrons through which K² isbound to M, said K² group containing up to 50 atoms not countinghydrogen atoms, and f is 1 or 2.

Further suitable procatalysts include a those disclosed in WO2017/173080 A1, which is incorporated by reference in its entirety. Suchprocatalysts include the metal-ligand complex of Formula (i):

wherein M is titanium, zirconium, or hafnium;

wherein each Z1 is independently a monodentate or polydentate ligandthat is neutral, monoanionic, or dianionic, wherein nn is an integer,and wherein Z1 and nn are chosen in such a way that the metal-ligandcomplex of Formula (i) is overall neutral;

wherein each Q¹ and Q¹⁰ independently is selected from the groupconsisting of (C₆-C₄₀)aryl, substituted (C₆-C₄₀)aryl,(C₃-C₄₀)heteroaryl, and substituted (C₃-C₄₀)heteroaryl;

wherein each Q², Q³, Q⁴, Q⁷, Q⁸, and Q⁹ independently is selected from agroup consisting of hydrogen, (C₁-C₄₀)hydrocarbyl, substituted(C₁-C₄₀)hydrocarbyl, (C₁-C₄₀)heterohydrocarbyl, substituted(C₁-C₄₀)heterohydrocarbyl, halogen, and nitro (NO₂);

wherein each Q⁵ and Q⁶ independently is selected from the groupconsisting of a (C₁-C₄₀)alkyl, substituted (C₁-C₄₀)alkyl, and[(Si)₁—(C+Si)₄₀] substituted organosilyl;

wherein each N independently is nitrogen;

optionally, two or more of the Q¹⁻⁵ groups can combine together to forma ring structure, with such ring structure having from 5 to 16 atoms inthe ring excluding any hydrogen atoms; and

optionally, two or more of the Q⁶⁻¹⁰ groups can combine together to forma ring structure, with such ring structure having from 5 to 16 atoms inthe ring excluding any hydrogen atoms.

The metal ligand complex of Formula (i) above, and all specificembodiments thereof herein, is intended to include every possiblestereoisomer, including coordination isomers, thereof.

The metal ligand complex of Formula (i) above provides for homoleptic aswell as heteroleptic procatalyst components.

In an alternative embodiment, each of the (C₁-C₄₀) hydrocarbyl and(C₁-C₄₀) heterohydrocarbyl of any one or more of Q¹, Q², Q³, Q⁴, Q⁵, Q⁶,Q⁷, Q⁸, Q⁹ and Q¹⁰ each independently is unsubstituted or substitutedwith one or more R^(S) substituents, and wherein each R^(S)independently is a halogen atom, polyfluoro substitution, perfluorosubstitution, unsubstituted (C₁-C₁₈)alkyl, (C₆-C₁₈)aryl, F₃C, FCH₂O,F₂HCO, F₃CO, (R^(C1))₃Si, (R^(C1))₃Ge, (R^(C1))O, (R^(C1))S,(R^(C1))S(O), (R^(C1))S(O)₂, (R^(C1))₂P, (R^(C1))₂N, (R^(C1))₂C═N, NC,NO₂, (R^(C1))C(O)O, (R^(C1))OC(O), (R^(C1))C(O)N(R^(C1)), or(R^(C1))₂NC(O), or two of the R^(S) are taken together to form anunsubstituted (C₁-C₁₈)alkylene where each R^(S) independently is anunsubstituted (C₁-C₁₈)alkyl, and wherein independently each R^(C1) ishydrogen, unsubstituted (C₁-C₁₈)hydrocarbyl or an unsubstituted(C₁-C₁₈)heterohydrocarbyl, or absent (e.g., absent when N comprises—N═). In particular embodiments, Q⁵ and Q⁶ are each independently(C₁-C₄₀) primary or secondary alkyl groups with respect to theirconnection to the amine nitrogen of the parent ligand structure. Theterms primary and secondary alkyl groups are given their usual andcustomary meaning herein; i.e., primary indicating that the carbon atomdirectly linked to the ligand nitrogen bears at least two hydrogen atomsand secondary indicates that the carbon atom directly linked to theligand nitrogen bears only one hydrogen atom.

Optionally, two or more Q¹⁻⁵ groups or two or more Q⁶⁻¹⁰ groups eachindependently can combine together to form ring structures, with suchring structures having from 5 to 16 atoms in the ring excluding anyhydrogen atoms.

In preferred embodiments, Q⁵ and Q⁶ are each independently (C₁-C₄₀)primary or secondary alkyl groups and most preferably, Q⁵ and Q⁶ areeach independently propyl, isopropyl, neopentyl, hexyl, isobutyl andbenzyl.

In particular embodiments, Q¹ and Q¹⁰ of the olefin polymerizationprocatalyst of Formula (i) are substituted phenyl groups; as shown inFormula (ii),

wherein J¹-J¹⁰ are each independently selected from the group consistingof R^(S) substituents and hydrogen; and wherein each R^(S) independentlyis a halogen atom, polyfluoro substitution, perfluoro substitution,unsubstituted (C₁-C₁₈)alkyl, (C₆-C₁₈)aryl, F₃C, FCH₂O, F₂HCO, F₃CO,(R^(C1))₃Si, (R^(C1))₃Ge, (R^(C1))O, (R^(C1))S, (R^(C1))S(O),(R^(C1))S(O)₂, (R^(C1))₂P, (R_(C1))₂N, (R^(C1))₂C═N, NC, NO₂,(R^(C1))C(O)O, (R^(C1))OC(O), (R^(C1))C(O)N(R^(C1)), or (R^(C1))₂NC(O),or two of the R^(S) are taken together to form an unsubstituted(C₁-C₁₈)alkylene where each R^(S) independently is an unsubstituted(C₁-C₁₈)alkyl, and wherein independently each R^(C1) is hydrogen,unsubstituted (C₁-C₁₈)hydrocarbyl or an unsubstituted(C₁-C₁₈)heterohydrocarbyl, or absent (e.g., absent when N comprises—N═). More preferably, J¹, J⁵, J⁶ and J¹⁰ of Formula (ii) are eachindependently selected from the group consisting of halogen atoms,(C₁-C₈) alkyl groups, and (C₁-C₈) alkoxyl groups. Most preferably, J¹,J⁵, J⁶ and J¹⁰ of Formula (ii) are each independently methyl; ethyl orisopropyl.

The term “[(Si)₁—(C+Si)₄₀] substituted organosilyl” means a substitutedsilyl radical with 1 to 40 silicon atoms and 0 to 39 carbon atoms suchthat the total number of carbon plus silicon atoms is between 1 and 40.Examples of [(Si)₁—(C+Si)₄₀] substituted organosilyl includetrimethylsilyl, triisopropylsilyl, dimethylphenylsilyl,diphenylmethylsilyl, triphenylsilyl, and triethylsilyl.

Preferably, there are no O—O, S—S, or O—S bonds, other than O—S bonds inan S(O) or S(O)₂ diradical functional group, in the metal-ligand complexof Formula (i). More preferably, there are no O—O, P—P, S—S, or O—Sbonds, other than O—S bonds in an S(O) or S(O)₂ diradical functionalgroup, in the metal-ligand complex of Formula (i).

M is titanium, zirconium, or hafnium. In one embodiment, M is titanium.In another embodiment, M is zirconium. In another embodiment, M ishafnium. In some embodiments, M is in a formal oxidation state of +2,+3, or +4. Each Z1 independently is a monodentate or polydentate ligandthat is neutral, monoanionic, or dianionic. Z1 and nn are chosen in sucha way that the metal-ligand complex of Formula (i) is, overall, neutral.In some embodiments each Z1 independently is the monodentate ligand. Inone embodiment when there are two or more Z1 monodentate ligands, eachZ1 is the same. In some embodiments the monodentate ligand is themonoanionic ligand. The monoanionic ligand has a net formal oxidationstate of −1. Each monoanionic ligand may independently be hydride,(C₁-C₄₀)hydrocarbyl carbanion, (C₁-C₄₀)heterohydrocarbyl carbanion,halide, nitrate, carbonate, phosphate, borate, borohydride, sulfate,HC(O)O⁻, alkoxide or aryloxide (RO⁻), (C₁-C₄₀)hydrocarbylC(O)O⁻,HC(O)N(H)⁻, (C₁-C₄₀)hydrocarbylC(O)N(H)⁻,(C₁-C₄₀)hydrocarbylC(O)N((C₁-C₂₀)hydrocarbyl)⁻, R^(K)R^(L)B⁻,R^(K)R^(L)N⁻, R^(K)O⁻, R^(K)S⁻, R^(K)R^(L)P⁻, or R^(M)R^(K)R^(L)Si⁻,wherein each R^(K), R^(L), and R^(M) independently is hydrogen,(C₁-C₄₀)hydrocarbyl, or (C₁-C₄₀)heterohydrocarbyl, or R^(K) and R^(L)are taken together to form a (C₂-C₄₀)hydrocarbylene or(C₁-C₄₀)heterohydrocarbylene and R^(M) is as defined above.

In some embodiments at least one monodentate ligand of Z1 independentlyis the neutral ligand. In one embodiment, the neutral ligand is aneutral Lewis base group that is R^(X1)NR^(K)R^(L), R^(K)OR^(L),R^(K)SR^(L), or R^(X1)PR^(K)R^(L), wherein each R^(X1) independently ishydrogen, (C₁-C₄₀)hydrocarbyl, [(C₁-C₁₀)hydrocarbyl]₃Si,[(C₁-C₁₀)hydrocarbyl]₃Si(C₁-C₁₀)hydrocarbyl, or(C₁-C₄₀)heterohydrocarbyl and each R^(K) and R^(L) independently is asdefined above.

In some embodiments, each Z1 is a monodentate ligand that independentlyis a halogen atom, unsubstituted (C₁-C₂₀)hydrocarbyl, unsubstituted(C₁-C₂₀)hydrocarbylC(O)O—, or R^(K)R^(L) N— wherein each of R^(K) andR^(L) independently is an unsubstituted (C₁-C₂₀)hydrocarbyl. In someembodiments each monodentate ligand Z1 is a chlorine atom,(C₁-C₁₀)hydrocarbyl (e.g., (C₁-C₆)alkyl or benzyl), unsubstituted(C₁-C₁₀)hydrocarbylC(O)O—, or R^(K)R^(L) N— wherein each of R^(K) andR^(L) independently is an unsubstituted (C₁-C₁₀)hydrocarbyl.

In some embodiments there are at least two Z1 s and the two Z1 s aretaken together to form the bidentate ligand. In some embodiments thebidentate ligand is a neutral bidentate ligand. In one embodiment, theneutral bidentate ligand is a diene of Formula(R^(D1))₂C═C(R^(D1))—C(R^(D1))═C(R^(D1))₂, wherein each R^(D1)independently is H, unsubstituted (C₁-C₆)alkyl, phenyl, or naphthyl. Insome embodiments the bidentate ligand is a monoanionic-mono(Lewis base)ligand. The monoanionic-mono(Lewis base) ligand may be a 1,3-dionate ofFormula (D): R^(E1)—C(O⁻)═CH—C(═O)—R^(E1) (D), wherein each R^(E1)independently is H, unsubstituted (C₁-C₆)alkyl, phenyl, or naphthyl. Insome embodiments the bidentate ligand is a dianionic ligand. Thedianionic ligand has a net formal oxidation state of −2. In oneembodiment, each dianionic ligand independently is carbonate, oxalate(i.e., ⁻O₂CC(O)O⁻), (C₂-C₄₀)hydrocarbylene dicarbanion,(C₁-C₄₀)heterohydrocarbylene dicarbanion, phosphate, or sulfate.

As previously mentioned, number and charge (neutral, monoanionic,dianionic) of Z1 are selected depending on the formal oxidation state ofM such that the metal-ligand complex of Formula (i) is, overall,neutral.

In some embodiments each Z1 is the same, wherein each Z1 is methyl;isobutyl; neopentyl; neophyl; trimethylsilylmethyl; phenyl; benzyl; orchloro. In some embodiments nn is 2 and each Z1 is the same.

In some embodiments at least two Z1 are different. In some embodiments,each Z1 is a different one of methyl; isobutyl; neopentyl; neophyl;trimethylsilylmethyl; phenyl; benzyl; and chloro.

In one embodiment, the metal-ligand complex of Formula (i) is amononuclear metal complex.

Further suitable procatalysts include those disclosed in Acc. Chem.Res., 2015, 48 (8), pp 2209-2220, including but not limited to those ofthe following structures:

Suitable procatalyst further include “single-component catalysts” thatcan catalyze olefin polymerization without the use of a co-catalyst.Such simple-component catalysts include those disclosed in Watson, P. L.J. Am. Chem. Soc. 1982,104, 337-339; Yasuda, H.; Ihara, E. Adv. Polym.Sci. 1997, 133, 53-101; Ihara, E.; Nodono, M.; Katsura, K.; Adachi, Y.;Yasuda, H.; Yamagashira, M.; Hashimoto, H.; Kanehisa, N.; and Kai, Y.Organometallics 1998, 17, 3945-3956; Long, D. P.; Bianconi, P. A. J. Am.Chem. Soc. 1996, 118, 12453-12454; Gilchrist, J. H.; Bercaw, J. E. J.Am. Chem. Soc. 1996, 118, 12021-12028; Mitchell, J. P.; Hajela, S.;Brookhart, S. K.; Hardcastle, K. I.; Henling, L. M.; Bercaw, J. E. J.Am. Chem. Soc. 1996, 118, 1045-1053; Evans, W. J.; DeCoster, D. M.;Greaves, J. Organometallics 1996, 15, 3210-3221; Evans, W. J.; DeCoster,D. M.; Greaves, J. Macromolecules 1995, 28, 7929-7936; Shapiro, P. J.;Cotter, W. D.; Schaefer, W. P.; Labinger, J. A.; Bercaw, J. E. J. Am.Chem. Soc. 1994, 116, 4623-4640; Schaverien, C. J. Organometallics 1994,13, 69-82; Coughlin, E. B. J. Am. Chem. Soc. 1992, 114, 7606-7607;Piers, W. E.; Bercaw, J. E. J. Am. Chem. Soc. 1990, 112, 9406-9407;Burger, B. J.; Thompson, M. E., Cotter, W. D.; Bercaw, J. E. J. Am.Chem. Soc. 1990, 112, 1566-1577; Shapiro, P. J.; Bunel, E.; Schaefer, W.P. Organometallics 1990, 9, 867-869; Jeske, G.; Lauke, H.; Mauermann,H.; Swepston, P. N.; Schumann, H.; Marks, T. J. J. Am. Chem. Soc. 1985,107, 8091-8103; Jeske, G.; Schock, L. E.; Swepston, P. N.; Schumann, H.;Marks, T. J. J. Am. Chem. Soc. 1985, 107, 8103-8110; andOrganometallics, 2001, 20 (9), pp 1752-1761. Exemplary, non-limitingformulas of such simple-component catalysts include:

wherein:

M is Sm or Y; and R is a monovalent ligand of up to 50 atoms notcounting hydrogen, preferably halide or hydrocarbyl.

Suitable procatalysts include but are not limited to the following namedas (Cat 1) to (Cat 17).

(Cat 1) may be prepared according to the teachings of WO 03/40195 andU.S. Pat. No. 6,953,764 B2 and has the following structure:

(Cat 2) may be prepared according to the teachings of WO 03/40195 and WO04/24740 and has the following structure:

(Cat 3) may be prepared according to methods known in the art and hasthe following structure:

(Cat 4) may be prepared according to the teachings of U.S. PatentApplication Publication No. 2004/0010103 and has the followingstructure:

(Cat 5) may be prepared according to the teachings of U.S. Pat. No.7,858,706 B2 and has the following structure:

(Cat 6) may be prepared according to the teachings of U.S. Pat. No.7,858,706 B2 and has the following structure:

(Cat 7) may be prepared by the teachings of U.S. Pat. No. 6,268,444 andhas the following structure:

(Cat 8) may be prepared according to the teachings of U.S. Pat. Pub. No.2003/004286 and has the following structure:

(Cat 9) may be prepared according to the teachings of U.S. Pat. Pub. No.2003/004286 and has the following structure:

(Cat 10) is commercially available from Sigma-Aldrich and has thefollowing structure:

(Cat 11) may be prepared according to the teachings of WO 2017/173080 A1and has the following structure:

(Cat 12) may be prepared according to the teachings of WO 2017/173080 A1and has the following structure:

(Cat 13) may be prepared according to the teachings of Macromolecules(Washington, D.C., United States), 43(19), 7903-7904 (2010) and has thefollowing structure:

(Cat 14) may be prepared according to the teachings of WO 2011/102989 A1and has the following structure:

(Cat 15) may be prepared according to the teachings of U.S. Pat. No.8,101,696 B2 and has the following structure:

(Cat 16) may be prepared according to the teachings of WO 2018/170138 A1and has the following structure:

(Cat 17) may be prepared according to the teachings of WO 2018/170138 A1and has the following structure:

In certain embodiments, the (c1) catalyst component comprises aprocatalyst and a co-catalyst. In these embodiments, the procatalyst maybe activated to form an active catalyst by combination with aco-catalyst (activator), preferably a cation forming co-catalyst, astrong Lewis acid, or a combination thereof.

Suitable cation forming co-catalysts include those previously known inthe art for metal olefin polymerization complexes. Examples includeneutral Lewis acids, such as C₁₋₃₀ hydrocarbyl substituted Group 13compounds, especially tri(hydrocarbyl)boron compounds and halogenated(including perhalogenated) derivatives thereof, having from 1 to 10carbons in each hydrocarbyl or halogenated hydrocarbyl group, moreespecially perfluorinated tri(aryl)boron compounds, and most especiallytris(pentafluoro-phenyl)borane; nonpolymeric, compatible,noncoordinating, ion forming compounds (including the use of suchcompounds under oxidizing conditions), especially the use of ammonium-,phosphonium-, oxonium-, carbonium-, silylium- or sulfonium-salts ofcompatible, noncoordinating anions, or ferrocenium-, lead- or silversalts of compatible, noncoordinating anions; and combinations of theforegoing cation forming cocatalysts and techniques. The foregoingactivating co-catalysts and activating techniques have been previouslytaught with respect to different metal complexes for olefinpolymerizations in the following references: EP-A-277,003; U.S. Pat.Nos. 5,153,157; 5,064,802; 5,321,106; 5,721,185; 5,350,723; 5,425,872;5,625,087; 5,883,204; 5,919,983; 5,783,512; WO 99/15534, and WO99/42467.

Combinations of neutral Lewis acids, especially the combination of atrialkyl aluminum compound having from 1 to 4 carbons in each alkylgroup and a halogenated tri(hydrocarbyl)boron compound having from 1 to20 carbons in each hydrocarbyl group, especiallytris(pentafluorophenyl)borane, further combinations of such neutralLewis acid mixtures with a polymeric or oligomeric alumoxane, andcombinations of a single neutral Lewis acid, especiallytris(pentafluorophenyl)borane with a polymeric or oligomeric alumoxanemay be used as activating cocatalysts. Exemplary molar ratios of metalcomplex:tris(pentafluorophenyl-borane:alumoxane are from 1:1:1 to1:5:20, such as from 1:1:1.5 to 1:5:10.

Suitable ion forming compounds useful as co-catalysts in one embodimentof the present disclosure comprise a cation which is a Brønsted acidcapable of donating a proton, and a compatible, noncoordinating anion,A⁻. As used herein, the term “noncoordinating” refers to an anion orsubstance which either does not coordinate to the Group 4 metalcontaining precursor complex and the catalytic derivative derived therefrom, or which is only weakly coordinated to such complexes therebyremaining sufficiently labile to be displaced by a neutral Lewis base. Anoncoordinating anion specifically refers to an anion which whenfunctioning as a charge balancing anion in a cationic metal complex doesnot transfer an anionic substituent or fragment thereof to said cationthereby forming neutral complexes. “Compatible anions” are anions whichare not degraded to neutrality when the initially formed complexdecomposes and are noninterfering with desired subsequent polymerizationor other uses of the complex.

Suitable anions are those containing a single coordination complexcomprising a charge-bearing metal or metalloid core which anion iscapable of balancing the charge of the active catalyst species (themetal cation) which may be formed when the two components are combined.Also, said anion should be sufficiently labile to be displaced byolefinic, diolefinic and acetylenically unsaturated compounds or otherneutral Lewis bases such as ethers or nitriles. Suitable metals include,but are not limited to, aluminum, gold and platinum. Suitable metalloidsinclude, but are not limited to, boron, phosphorus, and silicon.Compounds containing anions which comprise coordination complexescontaining a single metal or metalloid atom are, of course, well knownand many, particularly such compounds containing a single boron atom inthe anion portion, are available commercially.

In one aspect, suitable cocatalysts may be represented by the followinggeneral formula:

(L*-H)_(g) ⁺(A)^(g−), wherein:

-   -   L* is a neutral Lewis base;    -   (L*-H)+ is a conjugate Brønsted acid of L*;    -   A^(g−) is a noncoordinating, compatible anion having a charge of        g−, and g is an integer from 1 to 3.

More particularly, A^(g−) corresponds to the formula: [M′Q₄]⁻; wherein:

-   -   M′ is boron or aluminum in the +3 formal oxidation state; and    -   Q independently in each occurrence is selected from hydride,        dialkyl-amido, halide, hydrocarbyl, hydrocarbyloxide, halo        substituted-hydrocarbyl, halosubstituted hydrocarbyloxy, and        halo-substituted silylhydrocarbyl radicals (including        perhalogenated hydrocarbyl-perhalogenated hydrocarbyloxy- and        perhalogenated silylhydrocarbyl radicals), each Q having up to        20 carbons with the proviso that in not more than one occurrence        is Q halide. Examples of suitable hydrocarbyloxide Q groups are        disclosed in U.S. Pat. No. 5,296,433.

In an exemplary embodiment, g is one, that is, the counter ion has asingle negative charge and is A⁻. Activating cocatalysts comprisingboron which are particularly useful in the preparation of catalysts ofthis disclosure may be represented by the following general formula:(L*-H)+(BQ₄)⁻; wherein:

-   -   L* is as previously defined;    -   B is boron in a formal oxidation state of 3; and    -   Q is a hydrocarbyl-, hydrocarbyloxy-, fluorinated hydrocarbyl-,        fluorinated hydrocarbyloxy-, or fluorinated        silylhydrocarbyl-group of up to 20 nonhydrogen atoms, with the        proviso that in not more than one occasion is Q hydrocarbyl.

Especially useful Lewis base salts are ammonium salts, more preferablytrialkyl-ammonium salts containing one or more C₁₂₋₄₀ alkyl groups. Inthis aspect, for example, Q in each occurrence can be a fluorinated arylgroup, especially, a pentafluorophenyl group.

Illustrative, but not limiting, examples of boron compounds which may beused as an activating cocatalyst in the preparation of the improvedcatalysts of this disclosure include the tri-substituted ammonium saltssuch as:

-   trimethylammonium tetrakis(pentafluorophenyl)borate,-   triethylammonium tetrakis(pentafluorophenyl)borate,-   tripropylammonium tetrakis(pentafluorophenyl)borate,-   tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,-   tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate,-   N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,-   N,N-dimethylanilinium n-butyltris(pentafluorophenyl)borate,-   N,N-dimethylanilinium benzyltris(pentafluorophenyl)borate,-   N,N-dimethylanilinium tetrakis(4-(t-butyldimethylsilyl)-2,3,5,6    tetrafluorophenyl)borate,-   N,N-dimethylanilinium    tetrakis(4-(triisopropylsilyl)-2,3,5,6-tetrafluorophenyl)borate,-   N,N-dimethylanilinium    pentafluorophenoxytris(pentafluorophenyl)borate,-   N,N-diethylanilinium tetrakis(pentafluorophenyl)borate,-   N,N-dimethyl-2,4,6-trimethylanilinium    tetrakis(pentafluorophenyl)borate,-   dimethyloctadecylammonium tetrakis(pentafluorophenyl)borate,-   methyldioctadecylammonium tetrakis(pentafluorophenyl)borate;

a number of dialkyl ammonium salts such as:

-   di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate,-   methyloctadecylammonium tetrakis(pentafluorophenyl)borate,-   methyloctadodecylammonium tetrakis(pentafluorophenyl)borate, and-   dioctadecylammonium tetrakis(pentafluorophenyl)borate;

various tri-substituted phosphonium salts such as:

-   triphenylphosphonium tetrakis(pentafluorophenyl)borate,-   methyldioctadecylphosphonium tetrakis(pentafluorophenyl)borate, and-   tri(2,6-dimethylphenyl)phosphonium    tetrakis(pentafluorophenyl)borate;

di-substituted oxonium salts such as:

-   diphenyloxonium tetrakis(pentafluorophenyl)borate,-   di(o-tolyl)oxonium tetrakis(pentafluorophenyl)borate, and-   di(octadecyl)oxonium tetrakis(pentafluorophenyl)borate; and

di-substituted sulfonium salts such as:

-   di(o-tolyl)sulfonium tetrakis(pentafluorophenyl)borate, and-   methylcotadecylsulfonium tetrakis(pentafluorophenyl)borate.

Further to this aspect of the disclosure, examples of useful(L*-H)⁺cations include, but are not limited to,methyldioctadecylammonium cations, dimethyloctadecylammonium cations,and ammonium cations derived from mixtures of trialkyl amines containingone or two C₁₄-18 alkyl groups.

Another suitable ion forming, activating cocatalyst comprises a salt ofa cationic oxidizing agent and a noncoordinating, compatible anionrepresented by the formula:

(Ox ^(h+))_(g)(A^(g−))_(h), wherein:

-   -   Ox^(h+) is a cationic oxidizing agent having a charge of h+;    -   h is an integer from 1 to 3; and    -   A^(g−) and g are as previously defined.

Examples of cationic oxidizing agents include: ferrocenium,hydrocarbyl-substituted ferrocenium, Ag⁺, or Pb⁺². Particularly usefulexamples of A^(g−) are those anions previously defined with respect tothe Bronsted acid containing activating cocatalysts, especiallytetrakis(pentafluorophenyl)borate.

Another suitable ion forming, activating cocatalyst can be a compoundwhich is a salt of a carbenium ion and a noncoordinating, compatibleanion represented by the following formula:

[C]⁺A⁻

wherein:

[C]+ is a C₁₋₂₀ carbenium ion; and is a noncoordinating, compatibleanion having a charge of −1. For example, one carbenium ion that workswell is the trityl cation, that is triphenylmethylium.

A further suitable ion forming, activating cocatalyst comprises acompound which is a salt of a silylium ion and a noncoordinating,compatible anion represented by the formula:

(Q¹ ₃si)⁺A⁻

wherein:

Q¹ is C₁₋₁₀ hydrocarbyl, and A⁻ is as previously defined.

Suitable silylium salt activating cocatalysts include trimethylsilyliumtetrakispentafluorophenylborate, triethylsilyliumtetrakispentafluorophenylborate, and ether substituted adducts thereof.Silylium salts have been previously generically disclosed in J. Chem.Soc. Chem. Comm. 1993, 383-384, as well as in Lambert, J. B., et al.,Organometallics 1994, 13, 2430-2443. The use of the above silylium saltsas activating cocatalysts for addition polymerization catalysts is alsodescribed in U.S. Pat. No. 5,625,087.

Certain complexes of alcohols, mercaptans, silanols, and oximes withtris(pentafluorophenyl)borane are also effective catalyst activators andmay be used according to the present disclosure. Such cocatalysts aredisclosed in U.S. Pat. No. 5,296,433.

Suitable activating cocatalysts for use herein also include polymeric oroligomeric alumoxanes (also called aluminoxanes), especiallymethylalumoxane (MAO), triisobutyl aluminum modified methylalumoxane(MMAO), or isobutylalumoxane; Lewis acid modified alumoxanes, especiallyperhalogenated tri(hydrocarbyl)aluminum- or perhalogenatedtri(hydrocarbyl)boron modified alumoxanes, having from 1 to 10 carbonsin each hydrocarbyl or halogenated hydrocarbyl group, and mostespecially tris(pentafluorophenyl)borane modified alumoxanes. Suchco-catalysts are previously disclosed in U.S. Pat. Nos. 6,214,760,6,160,146, 6,140,521, and 6,696,379.

A class of co-catalysts comprising non-coordinating anions genericallyreferred to as expanded anions, further disclosed in U.S. Pat. No.6,395,671, may be suitably employed to activate the metal complexes ofthe present disclosure for olefin polymerization. Generally, theseco-catalysts (illustrated by those having imidazolide, substitutedimidazolide, imidazolinide, substituted imidazolinide, benzimidazolide,or substituted benzimidazolide anions) may be depicted as follows:

wherein:

A*⁺ is a cation, especially a proton containing cation, and can betrihydrocarbyl ammonium cation containing one or two C₁₀₋₄₀ alkylgroups, especially a methyldi(C₁₄₋₂₀ alkyl)ammonium cation,

Q³, independently in each occurrence, is hydrogen or a halo,hydrocarbyl, halocarbyl, halohydrocarbyl, silylhydrocarbyl, or silyl,(including for example mono-, di- and tri(hydrocarbyl)silyl) group of upto 30 atoms not counting hydrogen, such as C₁₋₂₀ alkyl, and

Q² is tris(pentafluorophenyl)borane or tris(pentafluorophenyl)alumane).

Examples of these catalyst activators includetrihydrocarbylammonium-salts, especially, methyldi(C₁₄₋₂₀alkyl)ammonium-salts of:

-   -   bis(tris(pentafluorophenyl)borane)imidazolide,    -   bis(tris(pentafluorophenyl)borane)-2-undecylimidazolide,    -   bis(tris(pentafluorophenyl)borane)-2-heptadecylimidazolide,    -   bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazolide,    -   bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolide,    -   bis(tris(pentafluorophenyl)borane)imidazolinide,    -   bis(tris(pentafluorophenyl)borane)-2-undecylimidazolinide,    -   bis(tris(pentafluorophenyl)borane)-2-heptadecylimidazolinide,    -   bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazolinide,    -   bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolinide,    -   bis(tris(pentafluorophenyl)borane)-5,6-dimethylbenzimidazolide,    -   bis(tris(pentafluorophenyl)borane)-5,6-bis(undecyl)benzimidazolide,    -   bis(tris(pentafluorophenyl)alumane)imidazolide,    -   bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolide,    -   bis(tris(pentafluorophenyl)alumane)-2-heptadecylimidazolide,    -   bis(tris(pentafluorophenyl)alumane)-4,5-bis(undecyl)imidazolide,    -   bis(tris(pentafluorophenyl)alumane)-4,5-bis(heptadecyl)imidazolide,    -   bis(tris(pentafluorophenyl)alumane)imidazolinide,    -   bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolinide,    -   bis(tris(pentafluorophenyl)alumane)-2-heptadecylimidazolinide,    -   bis(tris(pentafluorophenyl)alumane)-4,5-bis(undecyl)imidazolinide,    -   bis(tris(pentafluorophenyl)alumane)-4,5-bis(heptadecyl)imidazolinide,    -   bis(tris(pentafluorophenyl)alumane)-5,6-dimethylbenzimidazolide,        and    -   bis(tris(pentafluorophenyl)alumane)-5,6-bis(undecyl)benzimidazolide.

Other activators include those described in the PCT publication WO98/07515, such as tris(2,2′,2″-nonafluorobiphenyl)fluoroaluminate.Combinations of activators are also contemplated by the disclosure, forexample, alumoxanes and ionizing activators in combinations, see forexample, EP-A-0 573120, PCT publications WO 94/07928 and WO 95/14044,and U.S. Pat. Nos. 5,153,157 and 5,453,410. For example, and in generalterms, WO 98/09996 describes activating catalyst compounds withperchlorates, periodates and iodates, including their hydrates. WO99/18135 describes the use of organoboroaluminum activators. WO 03/10171discloses catalyst activators that are adducts of Brønsted acids withLewis acids. Other activators or methods for activating a catalystcompound are described in, for example, U.S. Pat. Nos. 5,849,852,5,859,653, and 5,869,723, in EP-A-615981, and in PCT publication WO98/32775. All of the foregoing catalyst activators as well as any otherknown activator for transition metal complex catalysts may be employedalone or in combination according to the present disclosure. In oneaspect, however, the co-catalyst can be alumoxane-free. In anotheraspect, for example, the co-catalyst can be free of anyspecifically-named activator or class of activators as disclosed herein.

In a further aspect, the molar ratio of procatalyst/co-catalyst employedgenerally ranges from 1:10,000 to 100:1, for example, from 1:5000 to10:1, or from 1:1000 to 1:1. Alumoxane, when used by itself as anactivating co-catalyst, can be employed in large quantity, generally atleast 100 times the quantity of metal complex on a molar basis.

Tris(pentafluorophenyl)borane, where used as an activating co-catalystcan be employed generally in a molar ratio to the metal complex of from0.5:1 to 10:1, such as from 1:1 to 6:1 and from 1:1 to 5:1. Theremaining activating co-catalysts are generally employed inapproximately equimolar quantity with the metal complex.

In exemplary embodiments of the present disclosure, the co-catalyst is[(C₁₆₋₁₈H₃₃₋₃₇)-2CH3NH] tetrakis(pentafluorophenyl)borate salt.

Suitable co-catalysts also include those disclosed in U.S. ProvisionalPat. App. Nos. 62/650,423, 62/650,412, and 62650453, which areincorporated herein by reference in their entirety. Such co-catalystsinclude those of the ionic complex comprising an anion and acountercation, the anion having the structure:

wherein: M is aluminum, boron, or gallium; n is 2, 3, or 4; each R isindependently selected from the group consisting of: radical (II) andradical (II):

each Y is independently carbon or silicon; each R¹¹, R¹², R¹³, R²¹, R²²,R²³, R²⁴, and R²⁵ is independently chosen from (C₁-C₄₀)alkyl,(C₆-C₄₀)aryl, —OR^(C), —O—, —SR^(C), —H, or —F, wherein when R is aradical according to radical (III), at least one of R²¹⁻²⁵ is ahalogen-substituted (C₁-C₄₀)alkyl, a halogen-substituted (C₆-C₄₀)aryl,or —F; and provided that: when each R is a radical (II) and Y is carbon,at least one of R¹¹⁻¹³ is a halogen-substituted (C₁-C₄₀)alkyl, ahalogen-substituted (C₆-C₄₀)aryl, or —F; or when M is aluminum and n is4 and each R is a radical (II), and each Y is carbon: each R¹¹, R¹², andR¹³ of each R is a halogen-substituted (C₁-C₄₀)alkyl, ahalogen-substituted (C₆-C₄₀)aryl, or —F; or a total number of halogenatoms in R¹¹, R¹², and R¹³ of each R is at least six; each X is amonodentate ligand independently chosen from halogen-substituted(C₁-C₂₀)alkyl, (C₁-C₂₀)alkyl, halogen-substituted (C₆-C₄₀)aryl,(C₆-C₄₀)aryl, triflate, or —S(O)₃; optionally, two groups R arecovalently connected; each R^(N) and R^(C) is independently(C₁-C₃₀)hydrocarbyl or —H.

Such co-catalysts further include the bimetallic activator complexcomprising an anion and a countercation, the anion having a structure:

where: each M is independently aluminum, boron, or gallium; L is chosenfrom a species having at least two Lewis basic sites; each Q isindependently a monodentate ligand; n is 0, 1, or 2, wherein when n is0, Q is not present; x is 0, 1, or 2, wherein when x is 0, Q is notpresent; each R is independently selected from the group consisting ofradical (II) and radical (III):

each Y is independently carbon or silicon; each R¹¹, R¹², R¹³, R²¹, R²²,R²³, R²⁴, and R²⁵, is independently chosen from (C₁-C₄₀)alkyl,(C₆-C₄₀)aryl, —H, —NR^(N) ₂, —OR^(C), —SR^(C), or halogen, wherein whenR is radical (II), at least one of R¹¹⁻¹³ is perhalogenated(C₁-C₄₀)alkyl, perhalogenated (C₆-C₄₀)aryl, or —F; and when R is radical(III), at least one of R²¹⁻²⁵ is perhalogenated (C₁-C₄₀)alkyl,perhalogenated (C₆-C₄₀)aryl, or —F; optionally, when n is 0 or 1, two Rgroups are covalently connected; and each R^(N) or R^(C) Isindependently (C₁-C₃₀)hydrocarbyl or —H.

Such co-catalysts further include the metallic activator comprising ananion and a countercation, the anion having a structure:

where: n is 0 or 1; each R is independently selected from the groupconsisting of radical (II) and radical (III):

each Y is independently carbon or silicon; each R¹¹, R¹², R¹³, R²¹, R²²,R²³, R²⁴, and R²⁵ is independently chosen from (C₁-C₄₀)alkyl,halogen-substituted (C₁-C₄₀)alkyl, (C₆-C₄₀)aryl, halogen-substituted(C₆-C₄₀)aryl, —OR^(C), —SR^(C), —H, —F or Cl, wherein at least one ofR¹¹⁻¹³ and one of R²¹⁻²⁵ is a halogen-substituted (C₁-C₄₀)alkyl, ahalogen-substituted (C₆-C₄₀)aryl, or —F; and each X is a monodentateligand independently chosen from halogen-substituted (C₁-C₂₀)alkyl orhalogen-substituted (C₆-C₄₀)aryl; optionally, two X groups arecovalently connected; each R^(C) is independently halogen-substituted(C₁-C₃₀)hydrocarbyl; provided that when the countercation is (Ph)₃C⁺,and the anion is Al(C₆F₅)₄.

(B) Curing Component

In certain embodiments, the curable composition of the presentdisclosure may comprise from 0.01 wt % to 20 wt % (or from 0.05 wt % to20 wt %, or from 1 wt % to 20 wt %, or from 5 wt % to 15 wt %, or from 5wt % to 10 wt %) of the (B) curing component comprising a crosslinkingagent, based on the total weight of the curable composition.

In certain embodiments, the (B) curing component further comprisesco-agents, curing additives, accelerators, and/or scorch inhibitors. Incertain embodiments, the (B) curing component comprises a crosslinkingagent and a co-agent. In further embodiments, the (B) curing componentcontains only the crosslinking agent.

Non-limiting examples of suitable cross-linking agents includeperoxides; phenols; azides; aldehyde-amine reaction products;substituted ureas; substituted guanidines; substituted xanthates;substituted dithiocarbamates; sulfur-containing compounds, such asthiazoles, sulfenamides, thiuramidisulfides, paraquinonedioxime,dibenzoparaquinonedioxime, sulfur; imidazoles; silanes; metal oxides,such as zinc, magnesium, and lead oxides; dinitroso compounds, such asp-quinone-dioxime and p,p′-dibenzoylquinone-dioxime; andphenol-formaldehyde resins containing hydroxymethyl or halomethylfunctional groups and combinations thereof. The suitability of any ofthese cross-linking agents will be largely governed by the choice ofpolymers, as is well known to those skilled in the compounding art.

The crosslinking agent may include one or more organic peroxidesincluding but not limited to alkyl peroxides, aryl peroxides,peroxyesters, peroxycarbonates, diacylperoxides, peroxyketals, cyclicperoxides, dialkyl peroxides, peroxy esters, peroxy Bicarbonates, orcombinations of two or more thereof. Examples of peroxides include butare not limited to di-tertbutyl peroxide, dicumyl peroxide,di(3,3,5-trimethyl hexanoyl)peroxide, t-butyl peroxypivalate, t-butylperoxyneodecanoate, di(sec-butyl)peroxydicarbonate, t-amylperoxyneodecanoate, 1,1-di-t-butyl peroxy-3,3,5-trimethylcyclohexane,t-butyl-cumyl peroxide,2,5-dimethyl-2,5-di(tertiary-butyl-peroxyl)hexane,1,3-bis(tertiary-butyl-peroxyl-isopropyl)benzene, or a combinationthereof. An exemplary crosslinking agent is dicumyl peroxidecommercially available under the tradename LUPEROX® from Arkema or thetradename TRIGONOX® from Akzo Nobel. A further exemplary crosslinkingagent is VAROX® DBPH-50 from Vanderbilt Chemicals. When thecross-linking agent is a peroxide, certain processing aids and cureactivators such as stearic acid and ZnO may also be used.

When peroxide based curing agents are used, co-activators or coagentsmay be used in combination therewith. Suitable coagents include but arenot limited trimethylolpropane triacrylate (TMPTA), trimethylolpropanetrimethacrylate (TMPTMA), triallyl cyanurate (TAC), triallylisocyanurate (TALC), and 1,4-phenylenedimaleimide (available from TCIChemicals).

Suitable coagents further include but are not limited to thealkenyl-functional monocyclic organosiloxanes disclosed in WO2019/000311 and WO 2019/000654, which are incorporated herein byreference in their entirety. For example, the coagent may be amonocyclic organosiloxane of the formula [R1,R2SiO2/2]n, whereinsubscript n is an integer greater than or equal to 3; each R1 isindependently a (C2-C4)alkenyl or a H2C═C(R1a)-C(═O)—O—(CH2)_(m)—wherein R1a is H or methyl and subscript m is an integer from 1 to 4;and each R2 is independently H, (C1-C4)alkyl, phenyl, or R1. Examples ofsuch monocyclic organosiloxanes include but are not limited to2,4,6,8-tetramethyl-2,4,6,8-tetravinyl cyclotetrasiloxane,2,4,6-trimethyl-2,4,6-trivinyl-cyclotrisiloxane, or a combinationthereof.

A scorch inhibitor/retardant is a molecule that inhibits prematurecuring, or a collection of such molecules. Examples of a scorchinhibitor/retardant are hindered phenols; semihindered phenols; TEMPO;TEMPO derivatives; 1,1-diphenylethylene; 2,4-diphenyl-4-methyl-1-pentene(also known as alpha-methyl styrene dimer or AMSD); and allyl-containingcompounds described in U.S. Pat. No. 6,277,925B1, column 2, line 62, tocolumn 3, line 46.

Suitable cross-linking agents include those that are sulfur based, suchas elemental sulfur. When sulfur based curing agents are employed,accelerators and cure activators may be used as well, such as amines,disulfides, guanidines, thioureas, thiazoles, thiurams, sulfenamides,dithiocarbamates, xanthates, 4,4′-dithiodimorpholine, thiuram di- andpolysulfides, alkylphenol disulfides, and2-morpholino-dithiobenzothiazole, tetramethylthiuram disulfide (TMTD),dipentamethylenethiuram tetrasulfide (DPTT), 2-mercaptobenzothiazole(MBT), 2-mercaptobenzothiazolate disulfide (MBTS),zinc-2-mercaptobenozothiazolate (ZMBT), zinc diethyldithiocarbamatezinc(ZDEC), zinc dibutyldithiocarbamate (ZDBC), dipentamethylenethiuramtetrasulfide (DPTT), N-t-butylbenzothiazole-2-sulfanamide (TBBS), andmixtures thereof.

Additional crosslinking agents include, but are not limited to, phenolicresins, azides, aldehyde-amine reaction products, vinyl silanes,hydrosilylation agents, substituted ureas, substituted guanidines,substituted xanthates, substituted dithiocarbamates, and combinationsthereof. The crosslinking agent may be a phenolic curing agent or aperoxide curing agent, with an optional co-agent, or hydrosilylationcross-linking agent with a hydrosilylation catalyst, or dibutyl tindilaurate (“DBTDL”), with an optional co-agent alumina trihydrate(“ATH”). Popular industrial catalysts are “Speier's catalyst,” H₂PtCl₆,and Karstedt's catalyst, an alkene-stabilized platinum(O) catalyst.

When a cross-linking agent is used, the cross-linking can be induced byactivating the cross-linking agent in the curable formulation. Thecross-linking agent can be activated by exposing it to a temperatureabove its decomposition temperature. Temperatures range from 50° C. to300° C., such as 80° C. to 275° C. Time can be determined by one ofordinary skill in the art depending on polymers and cure componentsselected.

Alternatively, the cross-linking agent can be activated by exposing itto a radiation that causes the generation of free radicals from thecross-linking agent. Non-limiting examples of suitable radiation includeUV or visible radiation, electron beam or beta ray, gamma rays, X-rays,or neutron rays. Radiation is believed to activate the cross-linking bygenerating radicals in the polymer which may subsequently combine andcross-link. Radiation dosage depends upon many factors and can bedetermined by those skilled in the art. UV or visible radiationactivation can occur when the cross-linking agent is a peroxidephotoinitiator, such as dibenzoyl peroxide, cumene hydroperoxide,di-t-butyl peroxide, diacetyl peroxide, hydrogen peroxide,peroxydisulfates, and 2,2-bis(terbutylperoxy)-2,5-dimethylhexane.

In some embodiments, dual cure systems, which comprises at least twoactivation methods, may be effectively employed, such as combinationsselected from heat, moisture cure, and radiation. For instance, it maybe desirable to employ a peroxide cross-linking agent in conjunctionwith a silane cross-linking agent, a peroxide cross-linking agent inconjunction with radiation, a sulfur-containing cross-linking agent inconjunction with a silane cross-linking agent, or the like. Thoseskilled in the art will be readily able to select the amount ofcross-linking agent, based on the desired cross-linking level, thecharacteristics of the polymer such as molecular weight, molecularweight distribution, comonomer content, the presence of cross-linkingenhancing coagents, other additives and the like.

When the (A) polyolefin component is at least partially crosslinked, thedegree of crosslinking may be measured by dissolving the composition ina solvent for specified duration, and calculating the percent gel orunextractable component. The percent gel normally increases withincreasing crosslinking levels. For cured articles according to theinvention, the percent gel content may be from 5 to 100 percent, or from10 to 95 percent, or from 20 to 90 percent, or from 30 to 85 percent, orfrom 40 to 80 percent.

Applications and End Uses

The compositions of the present disclosure can be employed in a varietyof conventional fabrication processes to produce useful articles,including objects prepared by cast, blown, calendered, or extrusionprocesses; molded articles, such as blow molded, injection molded, orrotomolded articles; extrusions; fibers; and woven or non-woven fabrics.Compositions of the present disclosure can further include but are notlimited to other natural or synthetic polymers, oils, UV stabilizers,pigments, tackifiers, fillers (such as talc, calcium carbonate, glassfiber, carbon fiber), additives, reinforcing agents such as calcium ormagnesium carbonate, fatty acids and salts thereof, ignition resistantadditives, scorch inhibitors, antioxdiants, stabilizers, colorants,extenders, carbon black, crosslinkers, blowing agents, activators suchas zinc oxide or zinc stearate, silica, aluminum silicates, plasticizerssuch as dialkyl esters of dicarboxylic acids, antidegradants, softeners,waxes, (poly)alcohols, (poly)alcohol ethers, polyesters, metal salts,scavengers, nucleating agents, stability control agents, flameretardants, lubricants, processing aids, extrusion aids, and chemicalprotectors.

Of particular utility are curable formulations comprising the (A)polyolefin component. In some embodiments, the curable formulationscomprising the (A) polyolefin component may be cured via ebeaming(electron beaming) without needing a cross-linking agent. In furtherembodiments, the curable formulations further comprise cross-linkingagents and may also comprise co-agents, curing additives, scorchinhibitors, and/or accelerants. The curable formulations furthercomprising a cross-linking agent may be rheology modified by curing viaebeaming.

Fibers may be prepared from the present compositions. Fibers that may beprepared include staple fibers, tow, multicomponent, sheath/core,twisted, and monofilament. Suitable fiber forming processes includespinbonded, melt blown techniques, as disclosed in U.S. Pat. Nos.4,430,563, 4,663,220, 4,668,566, and 4,322,027, gel spun fibers asdisclosed in U.S. Pat. No. 4,413,110, woven and nonwoven fabrics, asdisclosed in U.S. Pat. No. 3,485,706, or structures made from suchfibers, including blends with other fibers, such as polyester, nylon orcotton, thermoformed articles, extruded shapes, including profileextrusions and co-extrusions, calendared articles, and drawn, twisted,or crimped yarns or fibers. The new polymers described herein are alsouseful for wire and cable coating operations, as well as in sheetextrusion for vacuum forming operations, and forming molded articles,including the use of injection molding, blow molding process, orrotomolding processes. Compositions can also be formed into fabricatedarticles such as those previously mentioned using conventionalpolyolefin processing techniques which are well known to those skilledin the art of polyolefin processing.

Dispersions (both aqueous and non-aqueous) can also be formed using thepresent formulations comprising the same.

Additives and adjuvants may be included in any formulation. Suitableadditives include fillers, such as organic or inorganic particles,including clays, talc, titanium dioxide, zeolites, powdered metals,organic or inorganic fibers, including carbon fibers, silicon nitridefibers, steel wire or mesh, and nylon or polyester cording, nano-sizedparticles, clays, and so forth; tackifiers, oil extenders, includingparaffinic or napthelenic oils; and other natural and syntheticpolymers, including other polymers according to the invention.

Suitable polymers for blending (and for inclusion in the (A) polyolefincomponent) include thermoplastic and non-thermoplastic polymersincluding natural and synthetic polymers. Such polymers includeunsaturated polyolefin thermoplastics (EPDM, polybutadiene, etc.),polyolefin thermoplastics with low or no unsaturations (PE, PP,ethylene/alpha-olefin interpolymers), other elastomers (SBCs, PVC, EVA,ionomers, etc.), and other engineering thermoplastics (styrenics,polyamides, polyesters, etc.). Exemplary polymers for blending includepolypropylene, (both impact modifying polypropylene, isotacticpolypropylene, atactic polypropylene, and random ethylene/propylenecopolymers), various types of polyethylene, including high pressure,free-radical LDPE, Ziegler Natta LLDPE, metallocene PE, includingmultiple reactor PE (“in reactor” blends of Ziegler-Natta PE andmetallocene PE, such as products disclosed in U.S. Pat. Nos. 6,545,088,6,538,070, 6,566,446, 5,844,045, 5,869,575, and 6,448,341),etlhylene-vinyl acetate (EVA), ethylene/vinyl alcohol copolymers,polystyrene, impact modified polystyrene, ABS, styrene/butadiene blockcopolymers and hydrogenated derivatives thereof (SBS and SEBS),ethylene-based olefin block copolymers (such as those available underthe trade name INFUSE™ available from the Dow Chemical Company),propylene-based olefin block copolymers (such as those available underthe trade name INTUNE™ available from the Dow Chemical Company), andthermoplastic polyurethanes. Homogeneous polymers such as olefinplastomers and elastomers, such as ethylene/alpha-olefin copolymers andpropylene-based copolymers with low or no unsaturations (for examplepolymers available under the trade designation VERSIFY™ available fromThe Dow Chemical Company, ENGAGE™ from The Dow Chemical Company, TAFMER™from Mitsui Chemicals, Exact™ from ExxonMobil, and VISTAMAXX™ availablefrom ExxonMobil) can also be useful as components in blends comprisingthe present polymers.

Suitable end uses include crosslinkable or non-crosslinkableformulations for films; fibers; soft touch goods, such as tooth brushhandles and appliance handles; gaskets and profiles; adhesives(functional adhesives, cross-linked adhesives, hot melt adhesives);footwear (including shoe soles and shoe liners); auto interior parts andprofiles; foam goods (both open and closed cell); impact modifiers forother thermoplastic polymers such as high density polyethylene,isotactic polypropylene, or other olefin polymers; coated fabrics;hoses; tubing; weather stripping; cap liners; flooring; construction orbuilding parts; woodworking; coatings (powder coatings, water-basedcoatings for beverage and food liners, solvent-based coatings forindustrial metal coatings); waterproofing; photovoltaic applications;wire and cable applications; thermoplastic vulcanizates (TPV)applications; EPDM thermosets; seals, belts, conveyor belts, automotivetiming belts and the like, gaskets, dampeners; tire compounds; highlyfilled compounds, sidewall and tread compounds; coagents for thermosetrubbers; crosslinked tubing; liquid (low viscosity) reaction injectionmolding; injection molded skins; 3D printing; and piping.

Compositions may also contain anti-ozonants or anti-oxidants that areknown to a rubber chemist of ordinary skill. The anti-ozonants may bephysical protectants such as waxy materials that come to the surface andprotect the part from oxygen or ozone or they may be chemical protectorsthat react with oxygen or ozone. Suitable chemical protectors includestyrenated phenols, butylated octylated phenol, butylateddi(dimethylbenzyl) phenol, p-phenylenediamines, butylated reactionproducts of p-cresol and dicyclopentadiene (DCPD), polyphenolicantioxidants, hydroquinone derivatives, quinoline, diphenyleneantioxidants, thioester antioxidants, and blends thereof. Somerepresentative trade names of such products are Wingstay™ S antioxidant,Polystay™ 100 antioxidant, Polystay™ 100 AZ antioxidant, Polystay™ 200antioxidant, Wingstay™ L antioxidant, Wingstay™ LHLS antioxidant,Wingstay™ K antioxidant, Wingstay™ 29 antioxidant, Wingstay™ SN-1antioxidant, and Irganox™ antioxidants. In some applications, theanti-oxidants and anti-ozonants used will preferably be non-staining andnon-migratory.

For providing additional stability against UV radiation, hindered aminelight stabilizers (HALS) and UV absorbers may be also used. Suitableexamples include Tinuvin™ 123, Tinuvin™ 144, Tinuvin™ 622, Tinuvin™ 765,Tinuvin™ 770, and Tinuvin™ 780, available from Ciba Specialty Chemicals,and Chemisorb™ T944, available from Cytex Plastics, Houston Tex., USA. ALewis acid may be additionally included with a HALS compound in order toachieve superior surface quality, as disclosed in U.S. Pat. No.6,051,681.

For some compositions, additional mixing process may be employed topre-disperse the anti-oxidants, anti-ozonants, carbon black, UVabsorbers, and/or light stabilizers to form a masterbatch, andsubsequently to form polymer blends there from.

Compositions according to the invention may also contain organic orinorganic fillers or other additives such as starch, talc, calciumcarbonate, glass fibers, polymeric fibers (including nylon, rayon,cotton, polyester, and polyaramide), metal fibers, flakes or particles,expandable layered silicates, phosphates or carbonates, such as clays,mica, silica, alumina, aluminosilicates or aluminophosphates, carbonwhiskers, carbon fibers, nanoparticles including nanotubes,wollastonite, graphite, zeolites, and ceramics, such as silicon carbide,silicon nitride or titanias. Silane based or other coupling agents mayalso be employed for better filler bonding. Non-limiting examples ofsuitable silane coupling agents include γ-chloropropyl trimethoxysilane,vinyl trimethoxysilane, vinyl triethoxysilane,vinyl-tris-(β-methoxy)silane, allyltrimethoxysilane,γ-methacryloxypropyl trimethoxysilane, β-(3,4-ethoxy-cyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyl trimethoxysilane,γ-mercaptopropyltrimethoxysilane, γ-aminopropyl trimethoxysilane,N-β-(aminoethyl)-γ-aminopropyl trimethoxysilane, and3-(trimethoxysilyl)propylmethacrylate, vinyl triacetoxysilane,γ-(meth)acryloxy, propyl trimethoxysilane, and combinations thereof.

Suitable blowing agents include but are not limited to inorganic blowingagents, organic blow agents, chemical blowing agents, and combinationsthereof. Non-limiting examples of suitable inorganic blowing agentsinclude carbon dioxide, nitrogen, argon, water, air, nitrogen, andhelium. Non-limiting examples of suitable organic blowing agents includealiphatic hydrocarbons having 1-6 carbon atoms, aliphatic alcoholshaving 1-3 carbon atoms, and fully and partially halogenated aliphatichydrocarbons having 1-4 carbon atoms. Non-limiting examples of suitablealiphatic hydrocarbons include methane, ethane, propane, n-butane,isobutane, n-pentane, isopentane, neopentane, and the like. Non-limitingexamples of suitable aliphatic alcohols include methanol, ethanol,n-propanol, and isopropanol. Non-limiting examples of suitable fully andpartially halogenated aliphatic hydrocarbons include fluorocarbons,chlorocarbons, and chlorofluorocarbons. Non-limiting examples ofsuitable fluorocarbons include methyl fluoride, perfluoromethane, ethylfluoride, 1,1-difluoroethane (HFC-152a), 1,1,1-trifluoroethane(HFC-143a), 1,1,1,2-tetrafluoro-ethane (HFC-134a), pentafluoroethane,difluoromethane, perfluoroethane, 2,2-difluoropropane,1,1,1-trifluoropropane, perfluoropropane, dichloropropane,difluoropropane, perfluorobutane, perfluorocyclobutane. Non-limitingexamples of suitable partially halogenated chlorocarbons andchlorofluorocarbons include methyl chloride, methylene chloride, ethylchloride, 1,1,1-tricliloroethane, 1,1-dichloro-1-fluoroethane (HCFC-14Ib), 1-chloro-1,1 difluoroethane (HCFC-142b),1,1-dichloro-2,2,2-trifluoroethane (HCFC-123) and1-chloro-1,2,2,2-tetrafluoroethane(HCFC-124). Non-limiting examples ofsuitable fully halogenated chlorofluorocarbons includetrichloromonofluoromethane (CFC-Il), dichlorodifluoromethane (CFC-12),trichlorotrifluoroethane (CFC-113), 1,1,1-trifluoroethane,pentafluoroethane, dichlorotetrafluoroethane (CFC-114),chloroheptafluoropropane, and dichlorohexafluoropropane. Non-limitingexamples of suitable chemical blowing agents include azodicarbonamide,azodiisobutyro-nitrile, benezenesulfonhydrazide, 4,4-oxybenzenesulfonyl-semicarbazide, p-toluene sulfonyl semi-carbazide, bariumazodicarboxylate, N,N′-dimethyl-N,N′-dinitrosoterephthalamide, andtrihydrazino triazine. In some embodiments, the blowing agent isazodicarbonamide isobutane, CO₂, or a mixture of thereof.

The (A) polyolefin component of the present disclosure can also bechemically modified, such as by grafting (for example by use of maleicanhydride (MAH), silanes, glycidyl methacrylate, or other graftingagent), halogenation, amination, sulfonation, or other chemicalmodification.

Testing Methods

Unless stated otherwise, the measurable properties discussed in theforegoing disclosure and the examples that follow are in accordance withthe following analytical methods.

Density

Samples that were measured for density were prepared according to ASTMD-1928, which is incorporated herein by reference in its entirety.Measurements were made within one hour of sample pressing using ASTMD-792, Method B, which is incorporated herein by reference in itsentirety.

Melt Index/Melt Flow Rate

Melt index (I2) was measured in accordance with ASTM D-1238, which isincorporated herein by reference in its entirety, Condition 190° C./2.16kg, and was reported in grams eluted per 10 minutes. Melt flow rate(I₁₀) was measured in accordance with ASTM D-1238, Condition 190° C./10kg, and was reported in grams eluted per 10 minutes.

GPC

Sample polymers were tested for their properties via GPC according tothe following.

A high temperature Gel Permeation Chromatography system (GPC IR)consisting of an Infra-red concentration detector (IR-5) fromPolymerChar Inc (Valencia, Spain) was used for Molecular Weight (MW) andMolecular Weight Distribution (MWD) determination. The carrier solventwas 1,2,4-trichlorobenzene (TCB). The auto-sampler compartment wasoperated at 160° C., and the column compartment was operated at 150° C.The columns used were four Polymer Laboratories Mixed A LS, 20 microncolumns. The chromatographic solvent (TCB) and the sample preparationsolvent were from the same solvent source with 250 ppm of butylatedhydroxytoluene (BHT) and nitrogen sparged. The samples were prepared ata concentration of 2 mg/mL in TCB. Polymer samples were gently shaken at160° C. for 2 hours. The injection volume was 200 μl, and the flow ratewas 1.0 ml/minute.

Calibration of the GPC column set was performed with 21 narrow molecularweight distribution polystyrene standards. The molecular weights of thestandards ranged from 580 to 8,400,000 g/mol, and were arranged in 6“cocktail” mixtures, with at least a decade of separation betweenindividual molecular weights.

The GPC column set was calibrated before running the examples by runningtwenty-one narrow molecular weight distribution polystyrene standards.The molecular weight (Mw) of the standards ranges from 580 to 8,400,000grams per mole (g/mol), and the standards were contained in 6 “cocktail”mixtures. Each standard mixture had at least a decade of separationbetween individual molecular weights. The standard mixtures werepurchased from Polymer Laboratories (Shropshire, UK). The polystyrenestandards were prepared at 0.025 g in 50 mL of solvent for molecularweights equal to or greater than 1,000,000 g/mol and 0.05 g in 50 mL ofsolvent for molecular weights less than 1,000,000 g/mol. The polystyrenestandards were dissolved at 80° C. with gentle agitation for 30 minutes.The narrow standards mixtures were run first and in order of decreasinghighest molecular weight (Mw) component to minimize degradation. Thepolystyrene standard peak molecular weights were converted topolyethylene Mw using the Mark-Houwink constants. Upon obtaining theconstants, the two values were used to construct two linear referenceconventional calibrations for polyethylene molecular weight andpolyethylene intrinsic viscosity as a function of elution column.

The polystyrene standard peak molecular weights were converted topolyethylene molecular weights using the following equation (asdescribed in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621(1968)):

M _(polyethylene) =A(M _(polystyrene))^(B)  (1)

Here B has a value of 1.0, and the experimentally determined value of Ais around 0.41.

A third order polynomial was used to fit the respectivepolyethylene-equivalent calibration points obtained from equation (1) totheir observed elution volumes of polystyrene standards.

Number, weight, and z-average molecular weights were calculatedaccording to the following equations:

$\begin{matrix}{\overset{\_}{Mn} = \frac{\sum^{i}{Wf}_{i}}{\sum^{i}\left( {{Wf}_{i}/M_{i}} \right)}} & (2) \\{\overset{\_}{Mw} = \frac{\sum^{i}\left( {{Wf}_{i}*M_{i}} \right)}{\sum^{i}{Wf}_{i}}} & (3) \\{\overset{\_}{Mz} = \frac{\sum^{i}\left( {{Wf}_{i}*M_{i}^{2}} \right)}{\sum^{i}\left( {{{Wf}_{i}}_{i}*M_{i}} \right)}} & (4)\end{matrix}$

Where, Wf_(i) is the weight fraction of the i-th component and M_(i) isthe molecular weight of the i-th component.

The MWD was expressed as the ratio of the weight average molecularweight (Mw) to the number average molecular weight (Mn).

The accurate A value was determined by adjusting A value in equation (1)until Mw calculated using equation (3) and the corresponding retentionvolume polynomial, agreed with the known Mw value of 120,000 g/mol of astandard linear polyethylene homopolymer reference.

The GPC system consists of a Waters (Milford, Mass.) 150° C. hightemperature chromatograph (other suitable high temperatures GPCinstruments include Polymer Laboratories (Shropshire, UK) Model 210 andModel 220) equipped with an on-board differential refractometer (RI).Additional detectors could include an IR4 infra-red detector fromPolymer ChAR (Valencia, Spain), Precision Detectors (Amherst, Mass.)2-angle laser light scattering detector Model 2040, and a Viscotek(Houston, Tex.) 150R 4-capillary solution viscometer. A GPC with thelast two independent detectors and at least one of the first detectorsis sometimes referred to as “3D-GPC”, while the term “GPC” alonegenerally refers to conventional GPC. Depending on the sample, eitherthe 15-degree angle or the 90-degree angle of the light scatteringdetector was used for calculation purposes.

Data collection was performed using Viscotek TriSEC software, Version 3,and a 4-channel Viscotek Data Manager DM400. The system was equippedwith an on-line solvent degassing device from Polymer Laboratories(Shropshire, UK). Suitable high temperature GPC columns could be used,such as four 30 cm long Shodex HT803 13 micron columns or four 30 cmPolymer Labs columns of 20-micron mixed-pore-size packing (MixA LS,Polymer Labs). The sample carousel compartment was operated at 140° C.and the column compartment was operated at 150° C. The samples wereprepared at a concentration of 0.1 grams of polymer in 50 milliliters ofsolvent. The chromatographic solvent and the sample preparation solventcontain 200 ppm of butylated hydroxytoluene (BHT). Both solvents weresparged with nitrogen. The polyethylene samples were gently stirred at160° C. for four hours (4 h). The injection volume was 200 microliters(μL). The flow rate through the GPC was set at 1 mL/minute.

NMR (¹³C and ¹H)

Sample Preparation: For ¹³C NMR, a sample was prepared by addingapproximately 2.7 g of stock solvent to 0.20-0.40 g of sample in a 10 mmNMR tube. The stock solvent is tetrachlorethane-d2 containing 0.025Mchromium acetylacetonate (relaxation agent). The samples were capped andsealed with Teflon tape. The samples were dissolved and homogenized byheating the tube and its contents at 135-140° C.

Sample Preparation: For ¹H NMR, a sample was prepared by adding 130 mgof sample to 3.25 g of 50/50 by weighttetrachlorethane-d2/Perchloroethylene with 0.001 M Cr(AcAc)₃ in a 10 mmNMR tube. The samples were purged by bubbling N₂ through the solvent viaa pipette inserted into the tube for approximately 5 minutes to preventoxidation, capped, sealed with Teflon tape. The samples were heated andvortexed at 115° C. to ensure homogeneity.

Data Acquisition Parameters: For ¹³C NMR, the data was collected using aBruker 400/600 MHz spectrometer equipped with a Bruker high-temperatureCryoProbe (see Reference 1 noted below). The data was acquired using256-8000 transients per data file, a 7.3 sec pulse repetition delay (6sec delay+1.3 sec acq. time), 90 degree flip angles, and a modifiedinverse gated decoupling with a sample temperature of 120° C. (seeReference 2 noted below). All measurements were made on non-spinningsamples in locked mode. Samples were homogenized immediately prior toinsertion into the heated (125° C.) NMR Sample changer, and were allowedto thermally equilibrate in the probe for 7 minutes prior to dataacquisition.

Data Acquisition Parameters: ¹H NMR was performed on a Bruker AVANCE400/600 MHz spectrometer equipped with a Bruker high-temperatureCryoProbe and a sample temperature of 120° C. Two experiments were runto obtain spectra, a control spectrum to quantify the total polymerprotons, and a double presaturation experiment, which suppresses theintense polymer backbone peaks and enables high sensitivity spectra forquantitation of the end-groups. The control was run with ZG pulse, 4scans, SWH 10,000 Hz, AQ 1.64s, D₁ 14s. The double presaturationexperiment was run with a modified pulse sequence, 1c1prf2.zz1, TD32768, 100 scans, DS 4, SWH 10,000 Hz, AQ 1.64s, D₁ 1s, D₁₃ 13s.

Data Analysis: The comonomer content was analyzed with correspondingmatrix or algebra method. The unsaturation was analyzed with the methodin Reference 3 noted below.

-   Reference 1: Z. Zhou, R. Kuemmerle, J. C. Stevens, D. Redwine, Y.    He, X. Qiu, R. Cong, J. Klosin, N. Montañez, G. Roof, Journal of    Magnetic Resonance, 2009, 200, 328.-   Reference 2: Z. Zhou, R. Kümmerle, X. Qiu, D. Redwine, R. Cong, A.    Taha, D. Baugh, B. Winniford, Journal of Magnetic Resonance:    187 (2007) 225.-   Reference 3: Z. Zhou, R. Cong, Y. He, M. Paradkar, M. Demirors, M.    Cheatham, W. deGroot, Macromolecular Symposia, 2012, 312, 88.

Brookfield Viscosity

The Brookfield viscosity was measured at 177° C. in accordance with ASTMD-3236, using a Brookfield RV-DV-II-Pro viscometer and spindle SC-31.

GC/MS

Tandem gas chromatography/low resolution mass spectroscopy usingelectron impact ionization (EI) is performed at 70 eV on an AgilentTechnologies 6890N series gas chromatograph equipped with an AgilentTechnologies 5975 inert XL mass selective detector and an AgilentTechnologies Capillary column (HP1MS, 15 m×0.25 mm, 0.25 micron) withrespect to the following:

Programed Method: Oven Equilibration Time at 50° C. for 0.5 min

then 25° C./min to 200° C., and hold for 5 min

Run Time 11 min DSC

Differential Scanning calorimetry (DSC) was performed using a TAInstruments Discovery DSC, equipped with an RCS cooling unit and anautosampler. A nitrogen purge gas flow of 50 mL/min was used. The highermolecular weight samples (<50 dg/min melt index at 190° C.) were pressedinto a thin film, at 190° C., on a Carver Hydraulic press, at a pressureof 20,000 psi, and for a time of 4 minutes, followed by cooling at atemperature of 23° C., at a pressure of 20,000 psi for a time of 1minute. About 3-10 mg of material was cut from the pressed film,weighed, placed in a light aluminum pan, and crimped shut. For the lowmolecular weight samples (>50 dg/min melt index at 190° C.), about 3-10mg of material was cut from the as-received bale, weighed, placed in alight aluminum pan, and crimped shut. The thermal behavior of thesamples was investigated using the following temperature profile: thesample was rapidly heated to 180° C., and held isothermally for 5minutes. The sample was then cooled to −90° C., at 10° C./min, and heldisothermally for 5 minutes. The sample was then heated to 150° C. at 10°C./min. The cooling and second heating curves were used for analysis.The glass transition temperature (Tg), melting temperature (Tm), andheat of enthalpy (ΔHm) were obtained from the second heat data. Thecrystallization temperature (Tc) was obtained from the first cool data.The Tg was determined using the half-height method. The Tm and Tc weredetermined as the peak of the melting endotherm and crystallizationexotherm, respectively. The percent crystallinity is calculated bydividing the heat of fusion (Hf), determined from the second heat curve,by a theoretical heat of fusion of 292 J/g for PE, and multiplying thisquantity by 100 (for example, % cryst.=(Hf/292 J/g)×100 (for PE)). Ifthe example contains majority propylene, the theoretical heat of fusionof 165 J/g for PP is used.

DMS

Rheology was measured on an Advanced Rheometric Expansion System (ARES),equipped with “25 mm” stainless steel parallel plates. Constanttemperature dynamic frequency sweeps, in the frequency range of 0.1 to100 rad/s, were performed under nitrogen purge at 190° C. Samplesapproximately “25.4 mm in diameter” and “3.2 mm thick” were compressionmolded on a Carver hydraulic hot press at a temperature of 190° C., at apressure of 20,000 psi, for a time of four minutes, followed by coolingat a temperature of 23° C., at a pressure of 20,000 psi, for a time ofone minute. The sample was placed on the lower plate, and allowed tomelt for five minutes. The plates were then closed to a gap of 2.0 mm,and the sample trimmed to “25 mm in diameter.” The sample was allowed toequilibrate at 190° C. for five minutes, before starting the test. Thecomplex viscosity was measured at constant strain amplitude of 10%.Viscosity at 0.1 rad/s (V0.1) and at 100 rad/s (V100) are reported,along with the ratio (V0.1/V100) of the two viscosity values.

Rubber Process Analyzer

The cure kinetic profiles (also known as curing curves) of eachformulation at 180° C. were measured using an Alpha Technology RPA-2000or MDR-2000 instrument. A 4 gram sample of the resins was placed betweentwo pieces of polyester Melinex S films. Alternatively, resin waspunched from the compressed patty prepared using a Carver press at 20°C. and 200 psi obtained following the Haake blending procedure detailedbelow to about 4 g of material before being placed between two pieces ofpolyester Melinex S film. The test was carried out at 180° C. over aperiod of 30 minutes at a frequency of 1.67 Hz and a 0.5 degree angle.The rheology or curve of torque as a function of time for eachformulated composition was measured from samples of uncured blanket,which was then cured during the analysis. The visco-elastic properties,such as minimum S′ torque (ML), maximum S′ torque (MH), tan delta @ML,tan delta @MH, and time to reach a certain percentage of the cure state(for example, t90 corresponds to the time in minutes to reach the 90%state of cure), were measured during the cure cycle. Immediatelyfollowing curing the instrument was set to cool down to 70° C. then therheological properties of some formulations were evaluated at 70, 55,40, and 25° C. at a frequency of 1.67 Hz and a 0.2 degree angle. Theviscoelastic properties, such as G″, G′, tangent of the phase angle (TanD), and S″ torque were measured. Immediately following the temperaturesweep, a 16 step frequency sweep from 0.02 Hz to 15.92 Hz (0.02, 0.03,0.04, 0.06, 0.10, 0.16, 0.25, 0.40, 0.63, 1.00, 1.5, 2.52, 4.00, 6.34,10.04, 15.92 Hz) at 25° C. and a 0.2 degree angle recorded therheological properties at room temperature such as as G″, G′, tangent ofthe phase angle (Tan D), and S″ torque.

Gel Content

Gel content of the sample polymers were measured according to ASTMD-2765 procedure A using xylenes as solvent.

Compression Set

Compression set was measured according to ASTM D395 at 23° C. and 100°C. Disks of 29 mm (±0.5 mm) in diameter and 12.7 mm (±0.5 mm) thickness,were prepared as described under the section for compression moldingseen in the examples below. Each button sample was inspected fornotches, uneven thickness and inhomogeneity, and selected buttons(without those defects) were tested. Compression set was performed ontwo specimens for each sample, at the temperatures specified, and theaverage results of the two specimens was reported. The button sample wasplaced in the compression device having two metal plates that could bepressed together, and locked into place at 75% of the original height ofthe button sample. The compression device, with the compressed samples,was then placed in an oven, and equilibrated at the appropriatetemperature for a specified time (22 hrs for 23° C. or 100° C.). In thistest, the stress was released at the test temperature, and the thicknessof the sample was measured after a 30 minute equilibration period atroom temperature. Compression set is a measured of the degree ofrecovery of a sample following compression, and is calculated accordingto the equation CS=(H0−H2)/(H0−H1); where HO is the original thicknessof the sample, H1 is the thickness of the spacer bar used, and H2 is thefinal thickness of the sample after removal of the compressive force.

Tensile Strain-Stress Properties

Tensile properties were measured using specimens which were die cut,using a small “dog bone” shaped micro tensile die, having the dimensionsdescribed in ASTM D-1708. The die cut specimens were cut from thecompression molded plaques, which were prepared as described under theCompression Molding section. Tensile properties (50% modulus, 100%modulus, strain at break, and stress at break) were measured at roomtemperature, following the method ASTM D-412 on an INSTRON MODEL 1122,made by INSTRU-MET.

Shore A Hardness

Sample specimens were cut from compression molded plaques, which wereprepared as described in the compression molding section. Shore Ahardness was measured per ASTM D2240, on a Shore A Durometer Model 2000,made by INSTRON, with a Durometer Stand Model 902. This method permitshardness measurements, based on either initial indentation, orindentation after a specific period of time, or both. As used herein,the indentation was measured at a specified time of ten seconds.

Tear

Tear strength of the sample polymers were measured under ambientconditions according to ASTM D-624, Type C or to ASTM D-1938, trousertear (T-Tear). Specimens were cut from compression molded plaques usinga die and punch press.

EXAMPLES Preparation of Chain Transfer Agents (CTA's)

Unless otherwise noted, all starting reagents and materials wereobtained from Sigma-Aldrich. The procatalysts (Cat 1), (Cat 13), (Cat14), and (Cat 17), as well as any others, used in the examples below arethe same as those discussed previously and prepared according to themethods discussed previously. Procatalyst (Cat 1) may also be identifiedas[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl. “Cocat A” is the co-catalyst used in the examples below and isbis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-) amine.

Synthesis of tris(2-(cyclohex-3-en-1-yl)ethyl)aluminum (“CTA 1”). Anexemplary chain transfer agent of the present disclosure was prepared asfollows. In a drybox, 4-vinyl-1-cyclohexene (3.2 mL, 24.6 mmol) andtriisobutylaluminum (2.0 ml, 7.92 mmol) were added to 5 mL of decane ina vial equipped with a stirbar and a venting needle on the cap. Thismixture was heated at 120° C. with stirring for 3 hours. After 3 hours,a sample was dissolved in benzene-d6 for ¹H NMR analysis, and anotheraliquot was hydrolyzed with water and analyzed by GC/MS. ¹H NMR showedall vinyl groups reacted and the internal double bond remained (FIG.1A). GC/MS showed a clean peak at m/z of 110, consistent to themolecular weight of ethylcyclohexene (FIG. 1B). Accordingly, ¹H NMR andGC/MS confirmed the synthesis oftris(2-(cyclohex-3-en-1-yl)ethyl)aluminum (“CTA 1”) via non-limitingScheme 1.

Synthesis of tris(3,7-dimethyloct-6-en-1-yl)aluminum (“CTA 2”): In anitrogen-filled drybox, a 40 mL vial was equipped with a stirbar andcharged with DIBAL-H (8.10 mL, 9.64 mmol; 20 wt % solution in toluene)and citronellene (4.00 g, 28.93 mmol; mixture of isomers). The vial wasplaced in a heating block and a vent needle was inserted into theheadspace. The solution was heated at 110-112° C. for 9 hours giving acolorless transparent solution ([Al]=0.88 M). The material wasdetermined to be the desired product via ¹H NMR (FIG. 2) of an aliquotdissolved in C₆D₆ as well as the GC/MS of a hydrolyzed aliquot(m/z=140). Accordingly, ¹H NMR and GC/MS confirmed the synthesis oftris(3,7-dimethyloct-6-en-1-yl)aluminum (“CTA 2”) via non-limitingScheme 2.

Synthesis of hex-4-en-1-yldiisobutylaluminum (“CTA 3”): An exemplarychain transfer agent of the present disclosure was prepared as follows.In a nitrogen-filled drybox, DIBAL-H (0.800 g, 5.63 mmol) and1,4-hexadiene (0.65 mL, 5.63 mmol, d 0.710; mixture of cis and transisomers) were added to 3 mL of dry, degassed toluene. The reactionmixture was stirred at 25° C. for 14 hours. ¹H NMR analysis of ahydrolyzed sample (see hydrolysis procedure below) showed no reaction.The solution was heated at 60° C. with stirring for 22 hours. After thevial was allowed to cool to 25° C. an aliquot was hydrolyzed andanalyzed. Complete reaction was observed by ¹H NMR indicated by thedisappearance of the starting diene and appearance of signals consistentwith the hydrolysis products: isobutane and 2-hexene. Hydrolysis foranalysis was carried out by diluting ca 0.1 mL of the sample to ca 2 mLwith C₆D₆ in a vial, removing the sample from the glove box, and addingca 0.1 mL of nitrogen-purged water via syringe. After shaking the vialthe mixture was passed through a 0.45 μm syringe filter. The organicphase passes through more easily than the aqueous phase, allowing forquick isolation of the organic phase for analysis. The sample was thenmixed with a small amount of silica gel and filtered again. This helpsremove residual Al species that can cause gelation. Accordingly, ¹H NMRconfirmed the synthesis of hex-4-en-1-yldiisobutylaluminum (“CTA 3”) vianon-limiting Scheme 3.

Synthesis of bis(-2-ethylhex-4-en-1-yl)zinc (“CTA 4”): In anitrogen-filled drybox, diethylzinc (3.40 mL, 5.00 mmol, 20 wt % intoluene), 1,4-hexadiene (1.16 mL, 10.00 mmol, d 0.710; mixture of cisand trans isomers), and the activator [HNMe(C₁₈H₃₇)₂][B(C₆F₅)₄] (1.40mL, 0.09 mmol, 0.064 M in methylcyclohexane) were mixed in a vial. (Cat13) (0.045 g, 0.08 mmol)) was added as a solid and the reaction mixturewas stirred at 25° C. for 20 hours. ¹H NMR and GC/MS analysis of ahydrolyzed sample (see hydrolysis procedure below) showed completereaction. ¹H NMR indicated by the disappearance of the starting dieneand appearance of signals consistent with the hydrolysis product5-methylhept-2-ene. GC/MS showed the same expected hydrolysis product.Accordingly, ¹H NMR and GC/MS confirmed the synthesis ofbis(-2-ethylhex-4-en-1-yl)zinc (“CTA 4”) via non-limiting Scheme 4.

Synthesis of “CTA 5”: Diethylzinc (0.66 mL, 0.97 mmol; 1.47 M solutionin toluene), 4-vinylcyclohexene (1.77 mL, 13.58 mmol; d 0.832), theactivator ([HNMe(C₁H₃₇)₂][B(C₆F₅)₄]) solution in methylcyclohexane (0.60mL, 0.039 mmol; 0.0644M) and triethylaluminum (0.53 mL, 3.88 mmol; neat,93%) were dissolved in toluene (−10 mL). (Cat 13) (0.023 g, 0.039 mmol)was added as a solid and the reaction mixture was stirred at 25° C. for14 hours. An aliquot was dissolved in C₆D₆ and quenched with water.GC/MS and ¹H NMR confirmed the consumption of 4-vinylcyclohexene and theformation of the desired product (m/z=138). Accordingly, this confirmsthat CTA 5 was prepared via non-limiting Scheme 5.

Synthesis of “CTA 6”: The toluene solution oftris(2-(cyclohex-3-en-1-yl)ethyl)aluminum (10 mL, [Al]=0.424 M) wasmixed with diisobutylzinc (0.286 g, 1.59 mmol) and 4-vinylcyclohexene(0.416 mL, 3.19 mmol; d 0.830). The solution was heated for 4 hours at110° C. with a vent needle inserted through the septum cap of the vialto allow isobutylene to escape. During this treatment ^(i)Bu groups fromDIBZ transferred to Al and thermal elimination of isobutylene followedby 4-vinylcyclohexene insertions ensured that all alkyl groups on Al andZn were cyclohexenylethyl groups. An aliquot (0.1 mL) of this mixturewas diluted with C₆D₆ (0.5 mL) and hydrolyzed for ¹H NMR analysis. ¹HNMR analysis confirmed CTA was synthesized via non-limiting Scheme 6.

Synthesis of “CTA 7”: The synthesis of CTA 7 is exemplified innon-limiting Scheme 7 and described as follows. It was carried out intwo steps. In the first step, trivinylcyclohexane (TVCH) was convertedto a diene via intramolecular cyclization in the presence of catalyticamount of DIBAL-H, and in the second step additional DIBAL-H was addedto form the CTA. Thus, in a nitrogen-filled drybox, DIBAL-H (0.30 g,2.11 mmol) was added to TVCH (4.09 mL, 21.1 mmol; d 0.836). The mixturewas heated at 160° C. and stirred for 2h to form cyclized-TVCH. In aseparate vial additional DIBAL-H (0.35 g, 2.46 mmol) was dissolved indecane (5 mL), followed by addition of a portion of the cyclized-TVCH(2.05 mL, 10.5 mmol) obtained above. The solution was maintained at 130°C. for 2 h to obtain the Al-TVCH solution.

Synthesis of “CTA 8”: The synthesis of CTA 8 is exemplified innon-limiting Scheme 8 and described as follows. In a nitrogen-filleddrybox, a 20 mL vial was equipped with a stirbar and charged withDIBAL-H (2.00 mL, 2.39 mmol; 20 wt % in toluene (1.196 M)) and(R)-(+)-limonene (2.32 mL, 14.35 mmol; d 0.842). The vial was placed ina heating block, a vent needle was inserted through the septum cap, andthe solution was heated at 110112° C. for 11 hours. Solvent and excesslimonene were removed under vacuum at 50° C. overnight to afford thedesired product as a colorless viscous oil (0.870 g, 83%).

Synthesis of “CTA 9”: The synthesis of CTA 9 is exemplified innon-limiting Scheme 9 and described as follows. In a nitrogen-filleddrybox a 40 mL vial was equipped with a stirbar and charged with DIBAL-H(2.00 g, 14.06 mmol), toluene (9.2 mL) and 7-methyl-1,6-octadiene (5.24g, 42.19 mmol). An immediate exotherm (with some bubbling) was observed.The vial was placed in a heating block, a vent needle was insertedthrough the septum cap, and the solution was heated at 110-112° C. for 3hours. After 3 hours of reaction time an aliquot showed reactionprogress. The solution contained a small amount of suspended white solidparticles. The reaction was continued for another 22 hours. The reactionwas nearly complete. A small amount of dimer formation from the alkenereagent was observed. The reaction was continued for another 16 hours.Analysis of an aliquot showed no significant changes.

Batch Reactor Synthesis of Telechelic Polyolefins

Three sets of non-limiting examples of the telechelic polyolefin of theformula A¹L¹L²A² were synthesized via batch reactor as follows.

Set 1

With reference to Tables 1A-1C, Set 1 includes inventive telechelicpolymers made in runs BR1 to BR12 that were prepared as follows. In eachrun, a one gallon stirred autoclave reactor is charged with Isopar™ Emixed alkanes solvent (˜1.3 kg), desired mass of propylene, or octene,and/or ethylidene norbornene (ENB) (60 g) and CTA. The reactor is heatedto 120° C. and charged with ethylene (20 g). An active catalyst solutionis prepared in a drybox under inert atmosphere by mixing procatalyst andan activator mixture (a mixture of 1.2 equiv of Cocat A and 10 equiv ofmodified methyl aluminoxane (MMAO-3A)), where the active catalystsolution has a ratio of procatalyst to Cocat A of 1:1.2. The activecatalyst solution is injected into the reactor to initiate thepolymerization. The reactor pressure and temperature is kept constant byfeeding ethylene during the polymerization and cooling the reactor asneeded. After 10 minutes, the reactor was heated to 200° C. and kept atthe temperature for 20 minutes. The ethylene feed is shut off and thepolymer solution transferred into a nitrogen-purged resin kettle. Anadditive solution containing a phosphorus stabilizer and phenolicantioxidant (Irgafos® 168 and Irganox® 1010 in a 2:1 ratio by weight intoluene) is added to give a total additive content of approximately 0.1%in the polymer. The polymer is thoroughly dried in a vacuum oven.

TABLE 1A Step 1 Step 2 CTA 1 Ethylene Propylene Temp. Time Temp. TimeYield Efficiency Mn, Mw, Mw/ Run (mmol) (g) (g) (° C.) (min) (° C.)(min) (g) (g-Pol/g-M) g/mol g/mol Mn BRA 0 22 61 120 10 200 20 35.29,860 143,003 727,981 5.1 BR1 0.66 20 62 120 10 200 20 54.7 15,32329,864 109,316 3.7 BR2 1.33 19 62 120 10 200 20 60.5 16,948 19,72961,983 3.1 BR3 2 19 61 120 10 200 20 32.6 9,132 14,129 44,304 3.1 BR42.66 18 62 120 10 200 20 27.8 7,788 8,840 35,203 4.0

TABLE 1B Run BR5 BR6 BR7 BR8 BR9 BR10 BR11 BRB BR12 Catalyst Cat 1 Cat17 Cat 1 Cat 17 Cat 1 Cat 1 Cat 17 Cat A* Cat A* Catalyst (mmol) 0.030.0003 0.0065 0.031 0.035 0.0175 0.015 0.0006 0.0019 CTA CTA 1 CTA 1 CTA1 CTA 1 CTA 1 CTA 1 CTA 1 — CTA1 CTA (mmol) 10 0.68 10 6.3 10 10 0.68 06.3 Ethylene (g) 0 5.4 5.1 4 2.3 5.7 1.9 30.6 29 Propylene (g) 100 202301 150 — — — 102 101 Octene (g) — — — — 30 21 30 — — ENB (mL) — — — — —— — 4.4 4.4 Step 1 Temp. (° C.) 120 130 120 120 120 120 120 120 120 Step1 Time (min) 10 10 10 10 10 10 10 10 10 Step 2 Temp. (° C.) 200 200 200200 200 200 200 — 200 Step 2 Time (min) 20 20 20 20 20 20 20 — 20 Yield(g) 10.6 34.3 69.5 36.5 36.7 53.4 50.6 11.2 31.4 Efficiency 1,985642,322 60,069 6,615 5,891 17,143 18,951 205,128 181,608 (g-Pol/g-M)*Cat A =Zirconium,[2,2′′′-[1,3-propanediylbis(oxy-_(K)O)bis[3′′,5,5′′-tris(1,1-dimethylethyl)-5′-methyl[1,1′:3′,1′′-terphenyl]-2′-olato-_(K)O]]dimethyl-,(OC-6-33)-

TABLE 1C Run BR5 BR6 BR7 BR8 BR9 BR10 BR11 BRB BR12 Mn (g/mol) 2,759193,481 7,495 136,766 1,134 1,613 52,297 48,589  63,408 Mw (g/mol) 6,714524,693 26,840 282,774 2,270 5,474 159,337 95,524 147,907 Mw/Mn 2.432.71 3.58 2.07 2.00 3.39 3.05     1.97     2.33 13C NMR C2 mol % — 26.335.8 30.9 73.3 90.5 83.3    82.9    81.7 13C NMR C3 mol % 100.0 73.764.2 69.1 — — —    16.4    17.4 13C NMR C8 mol % — — — — 26.7 9.5 16.7 —— 13C NMR ENB mol % — — — — — — —     0.7     0.9 1H NMR #Vinyls/ 28 40551 62 5190 4806 139    35    152 1000000C 1H NMR #Vinylidenes/ 2695 33937 52 1971 800 23    31    66 1000000C 1H NMR #Vinylenes/ 215 20 6 0423 169 47    21    93 1000000C 1H NMR #Cyclohexenes/ 1853 10 1093 986767 5313 168 —    200 1000000C 1H NMR #Trisubstituted 0 3 0 0 47 32 4  4578   4119 alkenes/1000000C (including ENB) 1H NMR #Unsaturations/4.791 0.106 2.587 0.212 14.398 11.120 0.381     4.665     4.630 1000CCalculation Unsats/chain 1.42 2.00 1.83 2.79 2.10 1.65 2.14    17.92   23.41     0.33**     1.57** **Excluding ENB

Set 2

With reference to Table 2, Set 2 includes inventive telechelic polymersmade in runs B1-B7 via a similar procedure as Set 1. Run B1 used thescavenger MMAO-3A with a (Cat 1):Cocat A:scavenger ratio of 1:1.2:10.Runs B2 to B7 used a procatalyst to cocatalyst ratio of 1:1.2. All runsin Table 2 were carried out without hydrogen. All runs had the followingconditions: Ethylene (g): 20, 1-octene (g): 60, pressure (psi): 55,solvent (Isopar E, g): 1325. CTA 5 loading was based on the number oftransferrable groups. Runs B 1, B2, B4 and B6 were at 120° C. for 10min. Runs B3, B5 and B7 included an additional heating step at 200° C.for 20 min (excluding the transition time from 120 to 200° C.).

TABLE 2 Polymer Temp. Mn, Mw, Run Cat 1 CTA 5 (g) (° C.) g/mol g/molMw/Mn B1 4.5 — 43.0 120 72,542 739,532 10.2 B2 2.8 2 52.0 120 49,377208,606 4.2 B3 1.5 2 37.6 120 + 200 37,531 169,615 4.5 B4 2.5 4 86.0 12026,232 75,541 2.9 B5 1.5 4 76.0 120 + 200 22,630 78,956 3.5 B6 2.0 887.3 120 15,875 35,117 2.2 B7 1.0 8 119.0 120 + 200 12,239 31,477 2.6

Set 3

Set 3 includes the following examples to synthesize inventive telechelicpolyethylene polymers.

In a nitrogen-filled drybox, a vial equipped with a stir-bar is chargedwith octene (10 mL), Cocat A (0.023 mL of 0.075 M solution, 0.0017 mmol)and CTA 7 (0.402 mL of 0.5 M solution, 0.2 mmol). The vial is sealedwith a septum cap and placed in a heating block set to 100° C. Anethylene line (from a small cylinder) is connected and the vialheadspace is slowly purged via a needle. Cat 13 (0.067 mL of 0.02 Msolution, 0.0013 mmol) was injected, and the purge needle is removed tomaintain a total pressure at 20 psig. The polymerization was maintainedfor 20 min, then the ethylene line was removed and the polymer solutionwas cooled down. This polymer solution was transferred to a 600 mL Parrreactor and sealed. The reactor was heated to 200 degree C. under 200psig of ethylene pressure for 30 min. Polymer was quenched by largeamount of methanol, filtrated and dried under vacuum overnight. 1H NMR(FIG. 3) confirmed the synthesis occurred via the non-limiting reactionscheme shown below.

In a nitrogen-filled drybox, a vial equipped with a stir-bar is chargedwith octene (10 mL), Cocat A (0.023 mL of 0.075 M solution, 0.0017 mmol)and CTA 8 (0.088 g, 0.2 mmol). The vial is sealed with a septum cap andplaced in a heating block set to 100° C. An ethylene line (from a smallcylinder) is connected and the vial headspace is slowly purged via aneedle. Cat 13 (0.067 mL of 0.02 M solution, 0.0013 mmol) was injected,and the purge needle is removed to maintain a total pressure at 20 psig.The polymerization was maintained for 20 min, then the ethylene line wasremoved and the polymer solution was cooled down. This polymer solutionwas transferred to a 600 mL Parr reactor and sealed. The reactor washeated to 200 degree C. under 200 psig of ethylene pressure for 30 min.Polymer was quenched by large amount of methanol, filtrated and driedunder vacuum overnight. 1H NMR (FIG. 4) analysis confirmed the synthesisoccurred via the non-limiting reaction scheme below.

Continuous Solution Polymerization

Non-limiting examples of the telechelic polyolefin of the formulaA¹L¹L²A² and the unsaturated polyolefin of the formula A¹L¹ were madevia continuous solution polymerization as follows.

Continuous solution polymerizations are carried out in a computercontrolled autoclave reactor equipped with an internal stirrer. Purifiedmixed alkanes solvent (Isopar™ E available from ExxonMobil), monomers,and molecular weight regulator (hydrogen or chain transfer agent) aresupplied to a 3.8 L reactor equipped with a jacket for temperaturecontrol. The solvent feed to the reactor is measured by a mass-flowcontroller. A variable speed diaphragm pump controls the solvent flowrate and pressure to the reactor. At the discharge of the pump, a sidestream is taken to provide flush flows for the procatalyst, activator,and chain transfer agent (catalyst component solutions) injection lines.These flows are measured by Micro-Motion mass flow meters and controlledby control valves. The remaining solvent is combined with monomers andhydrogen and fed to the reactor. The temperature of the solvent/monomersolution is controlled by use of a heat exchanger before entering thereactor. This stream enters the bottom of the reactor. The catalystcomponent solutions are metered using pumps and mass flow meters and arecombined with the catalyst flush solvent and introduced into the bottomof the reactor. The reactor is liquid full at 500 psig with vigorousstirring. Polymer is removed through exit lines at the top of thereactor. All exit lines from the reactor are steam traced and insulated.The product stream is then heated at 230° C. by passing through a postreactor heater (PRH) where beta-H elimination of polymeryl-Al takesplace. A small amount of isopropyl alcohol is added along with anystabilizers or other additives either before the PRH (for thecomparative examples) or after the PRH (for the inventive examples)before devolatilization. The polymer product is recovered by extrusionusing a devolatilizing extruder.

The polymerization process conditions and results prior to post reactorheating (PRH) for the inventive and comparative examples are listed inTables Al to B2. Inventive unsaturated polyolefins of the formula A¹L¹are named as Inv. MP1 to MP4. Inventive telechelic polyolefins of theformula A¹L¹L²A² are named as Inv. TP1 to TP10. Comparative polymers arenamed as Comp. A and B. Additional abbreviations in the tables areexplained as follows: “Co.” stands for comonomer; “sccm” stands forstandard cm³/min; “T” refers to temperature; “Cat” stands forProcatalyst; “Cat 1” stands for Procatalyst (Cat 1); “Cat 17” stands forProcatalyst (Cat 17), “Cocat” stands for Cocat A; “Al CTA” stands foraluminum chain transfer agent”; “TEA” stands for triethylaluminum; “TOA”stands for trioctylaluminum, “Poly Rate” stands for polymer productionrate; “Cony” stands for percent ethylene conversion in reactor; and“Eff.” stands for efficiency, kg polymer/g catalyst metal.

In addition, [CTA]/[C₂H₄] refers to the molar ratio in reactor;Al/C_(2*1000)=(Al feed flow*Al concentration/1000000/Mw of Al)/(TotalEthylene feed flow*(1-fractional ethylene conversion rate)/Mw ofEthylene)*1000. “Al” in “Al/C_(2*1000)” refers to the amount of Al inthe CTA used in the polymerization process, and “C₂” refers to theamount of ethylene used in the polymerization process.

The properties of the inventive and comparative polymers following postreactor heating and recovery are provided in Tables C1-E2.

TABLE A1 C2 Co. Solv. H₂ T Cat. 1 Cat. 1 Flow Ex. lbs/hr Co. Type lbs/hrlbs/hr sccm ° C. ppm Hf lbs/hr Comp. A 1.375 Propylene 2.111 14.17 0 11565.8 0.220 Inv. MP1 1.556 Propylene 1.641 13.93 0 115 65.8 0.225 Comp. B1.520 Octene 1.362 14.98 352.7 115 65.8 0.286 Inv. MP2 1.521 Octene1.520 15.01 0 115 65.8 0.170 Inv. MP3 3.33 Octene 3.60 29.26 0 115 125.50.212 Inv. MP4 2.78 Octene 2.41 30.44 0 115 63.2 0.385

TABLE A2 CTA CTA Cocat A Poly Conc. Flow Cocat A Flow [C₂H₄]/ Rate ConvSolids Ex. CTA ppm A1 lbs/hr ppm lbs/hr [CTA] lbs/hr % % Eff. Comp. ATEA 10000 0.928 922 0.126 51.1 2.2 86.3 14.3 0.154 Inv. MP1 TEA 100001.14 922 0.129 143.5 2.2 94.7 14.1 0.148 Comp. B TEA 29.8 0.17 922 0.1640.0 2.1 90.9 12.6 0.11 Inv. MP2 TEA 10000 0.43 922 0.098 17.3 1.82 83 130.194 Inv. MP3 TEA 9827 0.744 925 0.232 20.7 4.47 89.0 13.7 0.168 Inv.MP4 TEA 1920 0.723 894 0.219 21.6 3.72 97.6 8.4 0.114

TABLE B1 C2 Co. Solv. H₂ T Cat. Conc. Cat. Flow Ex. Lbs/hr Co. Typelbs/hr lbs/hr sccm ° C. Cat ppm Hf lbs/hr Comp. A 1.375 Propylene 2.11114.17 0 115 Cat 1 65.8 0.22 Inv. TP1 1.555 Propylene 1.633 13.95 0 115Cat 1 65.8 0.334 Inv. TP2 1.52 Propylene 1.768 14.1 0 115 Cat 1 65.80.326 Comp. B 1.52 Octene 1.362 14.98 352.7 115 Cat 1 65.8 0.286 Inv.TP3 1.519 Octene 1.415 14.93 0 115 Cat 1 65.8 0.204 Inv. TP4 1.506Octene 1.657 19.44 0 115 Cat 1 65.8 0.18 Inv. TP5 2.78 Octene 2.62 25.50 115 Cat 1 63.2 0.475 Inv. TP6 4.76 Octene 5.46 41.78 0 118 Cat 1 125.50.328 Inv. TP7 2.56 Octene 3.39 17.40 0 115 Cat 1 125.5 0.199 Inv. TP83.84 Octene 1.07 42.19 0 125 Cat 14 54.2 0.149 Inv. TP9 2.78 Octene 2.6729.52 0 115 Cat 1 63.2 0.372 Inv. TP10 5.55 Octene 4.45 59.08 0 119 Cat1 63.2 1.002

TABLE B2 CTA CTA Cocat A Conc. Flow Cocat A Flow [C₂H₄]/ Poly Rate ConvSolids Ex. CTA ppm A1 lbs/hr ppm lbs/hr [CTA] lbs/hr % % Eff. Comp. ATEA 10000 0.928 922 0.126 51.1 2.2 86.3 14.3 0.154 Inv. TP1 CTA 1 691980.797 922 0.192 681.6 2.0 94.6 13 0.092 Inv. TP2 CTA 1 69198 0.78 9220.187 594.4 2.7 93.8 17.1 0.125 Comp. B TEA 29.8 0.17 922 0.164 0 2.190.9 12.6 0.11 Inv. TP3 CTA 1 69198 0.179 922 0.118 130.2 2.2 93.5 13.10.161 Inv. TP4 CTA 1 69198 0.077 922 0.103 33.1 2.0 88.9 9.7 0.174 Inv.TP5 CTA 2 2503 0.748 894 0.27 11.6 2.7 94.0 8.4 0.091 Inv. TP6 CTA 19432 0.420 925 0.359 7.8 6.4 88.9 13.8 0.157 Inv. TP7 CTA 1 18302 0.370925 0.218 76.3 3.8 96.4 19.0 0.151 Inv. TP8 CTA 1 1478 0.210 495 0.1310.8 3.5 89.8 7.5 0.431 Inv. TP9 CTA 1 3994 0.241 894 0.212 10.0 2.7 96.48.3 0.114 Inv. TP10 CTA 1 3994 0.467 894 0.570 11.6 5.5 97.0 8.6 0.087

TABLE C1 Method Property Units Comp. A Inv. MP1 Comp. B Inv. MP2 Inv.MP3 Inv. MP4 13C NMR % C2 mol % 70.1 76 89.4 88.7 89.1 88.3 13C NMR % C3mol % 29.9 24 — — — — 13C NMR % C8 mol % — — 10.6 11.3 10.9 11.7 1H NMRVinyls #/1000000C 27 1076 14 441 295 291 1H NMR Vinylidenes #/1000000C185 686 27 117 66 122 1H NMR Vinylenes #/1000000C 4 36 14 20 12 19 1HNMR Cyclohexenes #/1000000C 0 0 0 0 0 0 1H NMR Trisubstituted #/1000000C4 31 7 15 6 10 alkenes 13C NMR Saturated CH3 #/1000000C 2050 1810 — — —— NMR Unsaturations #/1000C 0.22 1.8 0.06 0.58 0.379 0.442 CalculationUnsats/chain #/chain 0.17 1.06 0.11 1.30 0.68 1.39 Density g/cc — —0.873 0.872 0.873 0.8715 Melt Index I2 at 190° C. dg/min — — 18.3 17.630.8 5.1 Melt Index I10/I2 at 190° C. — — 6.6 7.1 6.9 6.8 BrookfieldViscosity @ cP 11,687 6,952 — — — — 177° C.

TABLE C2 Method Property Units Comp. A Inv. MP1 Comp. B Inv. MP2 Inv.MP3 Inv. MP4 Conv. GPC Mn g/mol 9,244 7,239 19,618 22,862 18,823 32,689Conv. GPC Mw g/mol 20,993 16,847 52,931 56,983 50,945 79,030 Conv. GPCMz g/mol 44,770 34,657 92,282 122,456 129,351 157,436 Conv. GPC Mw/Mn2.27 2.33 2.7 2.49 2.71 2.42 DMS Viscosity at 0.1 Pa-s — — 348 479 —1513 rad/s (190° C.) DMS Viscosity at 100 Pa-s — — 279 303 — 725 rad/s(190° C.) DMS RR (V0.1/V100) — — 1.25 1.58 — 2.09 DMS Tan Delta at 0.1 —— 331 66.9 — 53.1 rad/s (190° C.) DMS Tan Delta at 100 — — 3.13 2.62 —1.68 rad/s (190° C.) DSC Tm ° C. −6.3 13.8 62.1 56.3 58.9 55.8 DSC Tc °C. −27.8 −3.5 48.6 61.2 68.3 61.7 DSC Heat of Fusion J/g 30.9 44.2 70.865 65.6 60.8 DSC Wt % Crystallinity % 10.6 15.1 24.3 22.3 22.5 20.8

TABLE D1 Polymer Properties Method Property Units Comp. A Inv. TP1 Inv.TP2 Comp. B Inv. TP3 Inv. TP4 13C NMR % C2 mol % 70.1 77.4 75.6 89.4 8988.9 13C NMR % C3 mol % 29.9 22.6 24.4 — — — 13C NMR % C8 mol % — — —10.6 11 11.1 13C NMR % ENB Mol % — — — — — — 1H NMR Vinyls #/1000000C 271262 1222 14 444 207 1H NMR Vinylidenes #/1000000C 185 677 722 27 101 861H NMR Vinylenes #/1000000C 4 62 63 14 28 23 1H NMR Cyclohexenes#/1000000C 0 1720 1680 0 450 215 1H NMR Trisubstituted #/1000000C 4 3734 7 8 7 alkenes 13C NMR Saturated CH3 #/1000000C 2050 640 440 — — — NMRUnsaturations #/1000C 0.22 3.72 3.69 0.06 1.02 0.53 CalculationUnsats/chain #/chain 0.17 2.07 2.13 0.11 2.22 2.24 Density g/cc — — —0.873 0.873 0.87 Melt Index I2 at 190° C. dg/min — — — 18.3 16.8 0.9Melt Index I10/I2 at 190° C. — — — 6.6 7 7.2 Brookfield Viscosity @ cP11,687 6,108 8,178 — — — 177° C.

TABLE D2 Polymer Properties Method Property Units Inv. TP5 Inv. TP6 Inv.TP7 Inv. TP8 Inv. TP9 Inv. TP10 13C NMR % C2 mol % 87.9 88.9 87.9 98.288.6 88.6 13C NMR % C3 mol % — — — — — — 13C NMR % C8 mol % 12.1 11.212.1 1.8 11.4 11.5 13C NMR % ENB Mol % — — — — — — 1H NMR Vinyls#/1000000C 285 471 1239 283 307 288 1H NMR Vinylidenes #/1000000C 97 101465 21 105 107 1H NMR Vinylenes #/1000000C 73 23 193 12 24 24 1H NMRCyclohexenes #/1000000C 474 1473 278 302 318 1H NMR Trisubstituted#/1000000C 242 9 110 0 10 7 alkenes 13C NMR Saturated CH3 #/1000000C — —— — — — NMR Unsaturations #/1000C 0.7 1.078 3.480 0.594 0.748 0.744Calculation Unsats/chain #/chain 2.2 1.97 2.34 1.71 2.36 2.42 Densityg/cc 0.869 0.873 0.869 0.922 0.872 0.872 Melt Index I2 at 190° C. dg/min5.4 27.3 — 1.9 4.7 5.3 Melt Index I10/I2 at 190° C. 6.7 6.7 — 7.4 6.86.7 Brookfield Viscosity @ cP — — 7906 — — — 177° C.

TABLE E1 Polymer Properties Method Property Units Comp. A Inv. TP1 Inv.TP2 Comp. B Inv. TP3 Inv. TP4 Conv. GPC Mn g/mol 9,244 6,925 7,14919,618 22,713 43,792 Conv. GPC Mw g/mol 20,993 16,138 16,622 52,93156,021 123,693 Conv. GPC Mz g/mol 44,770 39,246 47,921 92,282 129,181283,832 Conv. GPC Mw/Mn 2.27 2.33 2.33 2.7 2.47 2.83 DMS Viscosity at0.1 Pa-s — — — 348 490 9,312 rad/s (190° C.) DMS Viscosity at 100 Pa/s —— — 279 302 1,903 rad/s (190° C.) DMS RR (V0.1/V100) — — — 1.25 1.634.89 DMS Tan Delta at 0.1 — — — 331 52.9 10.1 rad/s (190° C.) DMS TanDelta at 100 — — — 3.13 2.65 0.934 rad/s (190° C.) DSC Tm ° C. −6.3 1710.1 62.1 58.4 53.3 DSC Tc ° C. −27.8 −0.1 −7 48.6 64.4 58.9 DSC Heat ofFusion J/g 30.9 51.9 39.6 70.8 69.6 60.2 DSC Wt % Crystallinity % 10.617.8 13.6 24.3 23.8 20.6

TABLE E2 Method Property Units Inv. TP5 Inv. TP6 Inv. TP7 Inv. TP8 Inv.TP9 Inv. TP10 Conv. GPC Mn g/mol 32,443 19,168 6,904 38,313 32,96833,937 Conv. GPC Mw g/mol 79,907 49,328 15,631 99,196 82,260 78,203Conv. GPC Mz g/mol 164,709 113,520 33,550 325,630 175,471 153,716 Conv.GPC Mw/Mn 2.46 2.57 2.26 2.59 2.50 2.30 DMS Viscosity at 0.1 Pa-s 1476 —— — 1735 — rad/s (190° C.) DMS Viscosity at 100 Pa/s 703 — — — 784 —rad/s (190° C.) DMS RR (V0.1/V100) 2.1 — — — 2.21 — DMS Tan Delta at 0.154.3 — — — 42.8 — rad/s (190° C.) DMS Tan Delta at 100 1.66 — — — 1.61 —rad/s (190° C.) DSC Tm ° C. 50 56.5 51.8 114.5 54.6 55.5 DSC Tc ° C.54.2 67.3 34.9 103.7 58.7 54.1 DSC Heat of Fusion J/g 55.2 69.3 55.7130.4 58.6 59.1 DSC Wt % Crystallinity % 18.9 23.7 19.1 44.7 20.1 20.2

As seen in the above tables, ¹H NMR and ¹³C NMR analyses confirm thesynthesis of new telechelic polyolefins TP1 to TP10 via the inventiveprocess of the present disclosure. Specifically, as one of ordinaryskill in the art would understand, ¹H NMR and ¹³C NMR analyses confirmformation of new telechelic polyolefins for TP1 to TP10, where suchpolyolefins have unsaturations at both ends. Specifically, suchpolyolefins have Al groups (vinyls, vinylenes, vinylidenes) on one endwith A² groups having hindered double bonds (cyclohexenes ortrisubstituted alkenes) on the other end. In contrast, comparativepolymers A and B, which were not prepared according to the inventiveprocess of the present disclosure, are polymers with low unsaturation asseen via ¹H NMR and ¹³C NMR analyses.

In Inv. TP5, the hindered double bond of the A2 group is atrisubstituted unsaturation, resulting in a high number oftrisubstituted unsaturations/1000000 C as reported in the above tables.The number of trisubstituted unsaturations in TP5 is higher than forComparative B that was produced with the same catalyst under similarreactor conditions, but with hydrogen to control molecular weight. Asmall number of trisubstituted unsaturations can be formed viabeta-hydride elimination and subsequent rearrangement of theunsaturation in an ethylene/alpha-olefin. The number of trisubstitutedunsaturations formed by this thermal termination mechanism is dependenton the catalyst and process conditions used. A small number oftrisubstituted unsaturations from this thermal termination mechanism ispresent in all of the comparative and inventive examples, but at a lowerlevel than the vinyls and vinylidenes, with the exception of TP5 wherethe majority of the trisubstituted unsaturations are from the A2 group.

As described above, the novel telechelic polyolefins of the presentdisclosure contain unsaturations at the termini of the chains ratherthan randomly distributed along the polymer backbone. Such telechelicpolyolefins may be suitable for curable formulations and may improvecrosslinking. By controlling the location of the unsaturations to thepolymer chain ends, a more controlled network structure is formed(uniform Mw between crosslinks) and more efficient use is made of theunsaturations on the polymer chain. This should provide better thermaland UV aging stability as less unsaturations are needed to form across-linked network with good mechanical properties for a givenmolecular weight. A low viscosity of a low Mw telechelic polyolefin ofthe present disclosure would provide excellent processability and flowprior to crosslinking, unlike high Mw EPDM.

In addition, the telechelic polyolefins of the present disclosure areproduced in a low cost solution polymerization from ethylene andalpha-olefins that is unique from telechelic polyolefins that have beenproduced in the literature via much more expensive and complicatedsynthetic routes. Further, the telechelic polyolefins also enable theopportunity for controlled chain extension to a higher molecular weightthermoplastic unlike random copolymers with unsaturations. Because theunsaturations are located at the chain ends, the telechelic polyolefinscan be chain extended to form a high molecular weight thermoplasticresin. Suitable crosslinking and chain extension chemistry includes, butis not limited to peroxide, thiolene, sulfur cure, phenolic cure, etc.

Curing Examples

Inventive curable formulations (Inv. 1A to 13A) including the inventivepolyolefins MP1 to MP4 and TP1 were prepared. Also prepared werecomparative formulations (Comp. A to W) including comparative polymers Aand B, as discussed above, as well as comparative polymers “0 ENB,” “1ENB,” “2.4 ENB,” “8.8 ENB,” “8100,” “8200”, “8407”.

Comparative polymers 0 ENB, 1 ENB, 2.4 ENB, and 8.8 ENB are EPDMpolymers prepared with increasing amounts of ethylidene norbornenemonomers and according to the process conditions of Table 3. For theprocess conditions of Table 3, “Cat B” is the procatalyst of Titanium,[N-(1,1-dimethylethyl)-1,1-dimethyl-1-[(1,2,3,3a,8a-.eta.)-1,5,6,7-tetrahydro-2-methyl-s-indacen-1-yl]silanaminato(2+.kappa.N][(1,2,3,4-.eta.)-1,3-pentadiene],“Cocat” is Cocat A from above, and “Cocat2” is Modified methylalumoxane(MMAO) Type 3A (no further purification performed) from Akzo Nobel, Inc.For comparative polymers 0 ENB, 1 ENB, 2.4 ENB, and 8.8 ENB, thesepolymers were measured as having about 0, 1, 2.4, and 8.8 units derivedfrom ENB monomers per chain, respectively.

Comparative polymers “8100”, “8200”, and “8407” are the polymersavailable as ENGAGE™ 8100, ENGAGE™ 8200, and ENGAGE™ 8407 available fromthe Dow Chemical Company. ENGAGE™ 8100 has a density of 0.870 g/cm³(ASTM D792) and a melt index of 1.0 g/10 min (ASTM D1238, 190° C./2.16kg). ENGAGE™ 8200 has a density of 0.870 g/cm³ (ASTM D792) and a meltindex of 5.0 g/10 min (ASTM D1238, 190° C./2.16 kg). ENGAGE™ 8407 has adensity of 0.870 g/cm³ (ASTM D792) and a melt index of 30 g/10 min (ASTMD1238, 190° C./2.16 kg).

The formulations Inv. 1A, 3A, 4A, and 5A and Comp. A-K were preparedaccording to the amounts listed in Tables 4 and 5 and according to thefollowing procedure. The polymer was weighed into a 250 mL wide mouthglass jar, then zinc oxide (ZnO) solid was added. The jar was placedinto a heating block that was set at 110° C. (leads to an internaltemperature of approximately 100° C.). The polymer and ZnO mixture waskept in the heating block for at least 45 minutes to soften the polymer.After this time a pre-weighed mixture of stearic acid,1,4-dimaleimidobenzene (1,4-DMB) or 1,3-dimaleimidobenzene (1,3-DMB;VANAX MBM) co-agent, and VAROX DBPH-50 peroxide was added to thepolymer, taking care to not get any of the solid on the walls of thejar. The contents of the jar were then mixed using an overhead stirrerequipped with a 4 blade 1.5 inch pitched blade turbine agitator. Themixing speeds and times were 25 rpm for 2 minutes, 100 rpms for 4minutes, and 175-200 rpm for 6 minutes. If it appeared there wereunmixed solids on the jar wall or the agitator shaft, the jar was raisedand lowered manually to promote incorporation of the solids. A heatresistant glove was used during this step, as the glass jar was hot.After the mixing, the jar was lowered, and the polymer that was still onthe agitator blade was allowed to drip back into the jar. The jar wasremoved using a heat resistant glove then placed upside down in a clamp,with the polymer collecting on a sheet of siliconized paper. After thepolymer flow from the jar minimized, the remaining polymer was isolatedfrom the jar using a silicon spatula. Typical recoveries were around90%. A portion of the polymer (about 4 grams) was then tested in therubber process analyser (RPA, see above for procedure). If the testcould not be completed the same day, the polymer was stored in a ziplocbag within a ziploc bag in a freezer set at −13° C. or lower.

Formulations Inv. 2A and 6A-13A and Comp. L-W were prepared according tothe amounts in Tables 4, 5, and 10 and according to the following Haakeblending procedure. Peroxide was VAROX DBPH-50 and co-agent was1,4-dimaleimidobenzene (1,4-DMB) or 1,3-dimaleimidobenzene (1,3-DMB;VANAX MBM). The blends were prepared using a RS5000 torque rheometerequipped with a Rheomix 600 Haake mixing bowl and standard rollerblades. The blends were mixed at 100° C. at 50 rpm for five minutes.During that time, the melt torque was monitored to ensure that thetorque reached a steady state after melting of the components. Thesample was immediately offloaded and compressed into a patty using aCarver press set at 20° C. and 200 psi for a time of three minutes. Aportion of the polymer (about 4 grams) was then tested in the rubberprocess analyzer (RPA, see above for procedure). If the test could notbe completed the same day, the polymer was stored in a 127iploc bagwithin a 127iploc bag in a freezer set at −13° C. or lower.

Following their preparation, the inventive and comparative formulationswere cured via heating at 180° C. for 30 minutes with the cure kineticsmeasured in accordance with the Rubber Process Analyzer method describedabove. Such cure kinetics are provided in Tables 6, 7, and 11, whererate of cure is calculated as (MH-ML)/(t90-t10).

Furthermore, physical properties of the inventive and comparativeformulations were measured in accordance with the methods describedabove and are presented in Tables 8, 9, and 11. The physical propertiesof the formulations were measured from plaques, cured in a compressionmolder (for tensile, compression set testing, C-tear, temperatureretraction). The samples were compression molded, in accordance to ASTMD3182, using a PHI (100 ton press). The desired mold (2 in. x 4 in., orcompression buttons) was placed on a platen. The sample (uncured patty)was cut slightly smaller than the dimensions of the individual moldcavity. The mold was spray brushed with a dilute solution of silicone.The platens were closed. The “normal” operating pressure was 100 tons,or as shown on the gauge as 200,000 pounds. When cure time ended, thebottom platen automatically opened. The samples were removed, andimmediately placed in water to stop the curing. Samples were conditionedfor 24 hours at room temperature, prior to testing. To cure the samples,the samples were conditioned at 180° C. using t95 data plus threeminutes for plaques, and using t95 data plus 15 minutes for compressionset buttons.

TABLE 3A C2 C3 ENB Solv. H₂ Reactor T Ex. lbs/hr lbs/hr lbs/hr lbs/hrsccm ° C. Comp - 0 ENB 3.72 3.67 0.00 29.31 722 140 Comp - 1 ENB 3.733.61 0.25 29.45 635 140 Comp - 2.4 ENB 3.73 3.55 0.31 29.47 590 140Comp - 8.8 ENB 3.89 2.70 0.66 30.00 580 140

TABLE 3B Cat B Cat B Cocat Cocat Cocat2 Cocat2 Poly Conc. Flow Conc.Flow Conc. Flow Rate Conv Solids Ex. metal ppm lbs/hr ppm lbs/hr Al ppmlbs/hr lbs/hr % % Eff. Comp - 0 ENB 14.0 0.312 309 0.428 157 0.316 5.4187.6 16.4 1.239 Comp - 1 ENB 14.0 0.325 309 0.444 157 0.330 5.64 87.317.0 1.242 Comp - 2.4 ENB 14.0 0.375 309 0.514 157 0.381 5.15 84.5 15.50.982 Comp - 8.8 ENB 41.7 0.296 1829 0.203 514 0.272 4.82 86.5 14.20.391

TABLE 4 Example Inv. 1A Inv. 2A Inv. 3A Inv. 4A Inv. 5A Inv 6A Inv 7AInv 8A Polymer 50/50 MP1 MP2 MP1 MP1 MP1/TP1 MP2 MP4 MP3 CurableCompositions (PHR) Polymer resin (PHR) 100 100 100 100 100 100 100 100Stearic Acid (PHR) 1.5 1.5 0.75 2.25 1.5 0.375 1.5 1.5 Zinc Oxide (PHR)5 5 2.5 7.5 5 1.25 5 5 Co-agent 1,4-DMB 1,4-DMB 1,4-DMB 1,4-DMB 1,4-DMB1,4-DMB 1,4-DMB 1,3-DMB Co-agent (PHR) 1 1 0.5 1.5 1 0.25 1 1 Peroxide(PHR) 6 6 3 9 6 1.5 6 6 Curable Compositions (wt %) Polymer resin (wt %)88.10 88.10 93.68 83.16 88.10 96.74 88.10 88.10 Stearic Acid (wt %) 1.321.32 0.70 1.87 1.32 0.36 1.32 1.32 Zinc Oxide (wt %) 4.41 4.41 2.34 6.244.41 1.21 4.41 4.41 Co-agent (wt %) 0.88 0.88 0.47 1.25 0.88 0.24 0.880.88 Peroxide (wt %) 5.29 5.29 2.81 7.48 5.29 1.45 5.29 5.29

TABLE 5A Example Comp. A Comp. B Comp. C Comp. D Comp. E Comp. F Comp. GComp. H Polymer A 0 ENB 1 ENB 2.4 ENB 8.8 ENB 1 ENB 2.4 ENB 8.8 ENBCurable Compositions (PHR) Polymer resin (PHR) 100 100 100 100 100 100100 100 Stearic Acid (PHR) 1.5 1.5 1.5 1.5 1.5 0.75 0.75 0.75 Zinc Oxide(PHR) 5 5 5 5 5 2.5 2.5 2.5 Co-agent 1,4-DMB 1,4-DMB 1,4-DMB 1,4-DMB1,4-DMB 1,4-DMB 1,4-DMB 1,4-DMB Co-agent (PHR) 1 1 1 1 1 0.5 0.5 0.5Peroxide (PHR) 6 6 6 6 6 3 3 3 Curable Compositions (wt %) Polymer resin(wt %) 88.10 88.10 88.10 88.10 88.10 93.68 93.68 93.68 Stearic Acid (wt%) 1.32 1.32 1.32 1.32 1.32 0.70 0.70 0.70 Zinc Oxide (wt %) 4.41 4.414.41 4.41 4.41 2.34 2.34 2.34 Co-agent (wt %) 0.88 0.88 0.88 0.88 0.880.47 0.47 0.47 Peroxide (wt %) 5.29 5.29 5.29 5.29 5.29 2.81 2.81 2.81

TABLE 5B Example Comp. I Comp. J Comp. K Comp. L Comp. M Comp. N Comp. OPolymer 1 ENB 2.4 ENB 8.8 ENB B 8100 8200 8407 Curable Compositions(PHR) Polymer resin (PHR) 100 100 100 100 100 100 100 Stearic Acid (PHR)2.25 2.25 2.25 1.5 1.5 1.5 1.5 Zinc Oxide (PHR) 7.5 7.5 7.5 5 5 5 5Co-agent 1,4-DMB 1,4-DMB 1,4-DMB 1,4-DMB 1,4-DMB 1,4-DMB 1,3-DMBCo-agent (PHR) 1.5 1.5 1.5 1 1 1 1 Peroxide (PHR) 9 9 9 6 6 6 6 CurableCompositions (wt %) Polymer resin (wt %) 83.16 83.16 83.16 88.10 88.1088.10 88.10 Stearic Acid (wt %) 1.87 1.87 1.87 1.32 1.32 1.32 1.32 ZincOxide (wt %) 6.24 6.24 6.24 4.41 4.41 4.41 4.41 Co-agent (wt %) 1.251.25 1.25 0.88 0.88 0.88 0.88 Peroxide (wt %) 7.48 7.48 7.48 5.29 5.295.29 5.29

TABLE 6 Example Inv. 1A Inv. 2A Inv. 3A Inv. 4A Inv. 5A Inv 6A Inv 7AInv 8A Polymer MP1 MP2 MP1 MP1 50/50 MP2 MP4 MP3 MP1/TP1 Cure CS1 CS1CS2 CS3 CS1 CS4 CS1 CS1 Package ML [dNm] −0.008 0.047 −0.008 −0.008−0.008 0.022 0.141 0.022 MH [dNm] 5.40 10.6 2.20 7.84 9.81 6.27 11.2910.09 MH-ML [dNm] 5.41 10.6 2.21 7.85 9.82 6.25 11.15 10.07 ts1 [min]2.29 0.48 5.68 1.50 2.04 1.03 0.42 0.53 ts2 [min] 3.23 0.61 14.1 1.992.58 1.51 0.52 0.69 t10 [min] 1.84 0.47 2.94 1.38 2.02 0.83 0.42 0.52t50 [min] 4.01 1.17 6.10 3.04 4.16 2.14 0.95 1.31 t90 [min] 10.1 4.2213.6 7.86 9.59 6.10 3.69 4.80 Rate of Cure dNm/min 0.65 2.83 0.21 1.211.30 1.19 3.41 2.35

TABLE 7A Example Comp. A Comp. B Comp. C Comp. D Comp. E Comp. F Comp. GComp. H Polymer A 0 ENB 1 ENB 2.4 ENB 8.8 ENB 1 ENB 2.4 ENB 8.8 ENB CurePackage CS1 CS1 CS1 CS1 CS1 CS2 CS2 CS2 ML (dNm) −0.008 −0.01 −0.008−0.006 −0.008 −0.01 −0.006 −0.01 MH (dNm) 0.792 0.514 2.50 5.21 9.930.392 0.916 2.31 MH − ML (dNm) 0.800 0.52 2.51 5.22 9.94 0.40 0.92 2.32ts1 (min) N/A 0 4.78 2.87 2.10 0 0 6.57 ts2 (min) N/A 0 9.65 4.09 2.77 00 14.8 t10 (min) 2.60 3.1 2.58 2.24 2.09 3.49 3.61 3.33 t50 (min) 6.167.18 5.61 4.91 4.78 8.09 7.59 7.30 t90 (min) 14.0 16.38 13.1 11.3 11.217.7 16.3 16.7 Rate of Cure 0.07 0.04 0.24 0.58 1.09 0.03 0.07 0.17(dNm/min)

TABLE 7B Example Comp. I Comp. J Comp. K Comp. L Comp. M Comp. N Comp. OPolymer 1 ENB 2.4 ENB 8.8 ENB B 8100 8200 8407 Cure Package CS3 CS3 CS3CS1 CS1 CS1 CS1 ML (dNm) −0.008 −0.008 −0.008 0.02 0.77 0.16 0.03 MH(dNm) 5.37 8.78 17.1 5.06 9.54 7.44 4.66 MH − ML (dNm) 5.38 8.79 17.15.04 8.76 7.28 4.64 ts1 (min) 2.44 1.75 1.21 1.11 0.33 0.53 1.30 ts2(min) 3.48 2.35 1.55 2.14 0.44 0.87 2.45 t10 (min) 1.92 1.66 1.45 0.640.31 0.45 0.69 t50 (min) 4.26 3.86 3.60 2.73 1.01 1.72 2.86 t90 (min)9.91 9.28 8.98 7.87 4.56 5.99 8.07 Rate of Cure 0.67 1.15 2.27 0.70 2.061.31 0.63 (dNm/min)

TABLE 8 Example Inv. 1A Inv. 2A Inv. 3A Inv. 4A Inv. 5A Inv 6A Inv 7AInv 8A Polymer MP1 MP2 MP1 MP1 50/50 MP2 MP4 MP3 MP1/TP1 Cure PackageCS1 CS1 CS2 CS3 CS1 CS4 CS1 CS1 RPA Tan Delta @ 0.156 0.053 0.213 0.1430.117 0.055 0.048 — 25° C. 1.67 Hz RPA Tan Delta @ 0.149 0.082 0.2690.108 0.098 0.140 0.070 — 70° C., 1.67 Hz 50% Modulus MPa 0.68 ± 0.012.43 ± 0.02 0.46 ± 0.01 0.73 ± 0.01 0.81 ± 0.01  2.52 ± 0.23 2.65 2.51 ±.06  100% Modulus MPa 0.90 ± 0.02 2.95 ± 0.03 0.61 ± 0.01  1.0 ± 0.021.10 ± 0.01  3.01 ± 0.24 3.23 2.95 ± 0.06 Stress @ Break MPa 1.41 ± 0.045.15 ± 0.2  1.40 ± 0.06 1.22 ± 0.06 1.36 ± 0.05 10.71 ± 0.76 5.46 2.22 ±0.87 Strain @ Break % 301 ± 14  344 ± 17  600 ± 45  164 ± 17  171 ± 12 709 ± 29 350 325 ± 72 

TABLE 9A Example Comp. A Comp. B Comp. C Comp. D Comp. E Comp. F Comp. GComp. H Polymer A 0 ENB 1 ENB 2.4 ENB 8.8 ENB 1 ENB 2.4 ENB 8.8 ENB CurePackage CS1 CS1 CS1 CS1 CS1 CS2 CS2 CS2 RPA Tan Delta @ 0.365 0.3450.243 0.189 0.133 0.349 0.322 0.278 25° C., 1.67 Hz RPA Tan Delta @0.351 0.463 0.213 0.129 0.066 0.463 0.354 0.218 70° C., 1.67 Hz 50%Modulus MPa N/A N/A 0.41 ± 0.01 0.47 ± 0.02 0.69 ± 0.02 N/A N/A 0.36 ±0.01 100% Modulus MPa N/A N/A 0.58 ± 0.01 0.69 ± 0.02 1.05 ± 0.03 N/AN/A 0.49 ± 0.01 Stress @ Break MPa N/A N/A 0.96 ± 0.08 0.94 ± 0.08 1.17± 0.07 N/A N/A 0.95 ± 0.03 Strain @ Break % N/A N/A 282 ± 44  176 ± 20 118 ± 11  N/A N/A 311 ± 16 

TABLE 9B Example Comp. I Comp. J Comp. K Comp. L Comp. M Comp. N Comp OPolymer 1 ENB 2.4 ENB 8.8 ENB B 8100     8200 8407 Cure Package CS3 CS3CS3 CS1 CS1 CS1 CS1 RPA Tan Delta @ 0.173 0.135 0.079 0.054 0.053 0.061— 25° C., 1.67 Hz RPA Tan Delta @ 0.113 0.078 0.041 0.159 0.082 0.111 —70° C., 1.67 Hz 50% Modulus MPa 0.55 ± 0.02 0.69 ± 0.02 1.02 ± 0.02 2.77± 0.07 2.39 ± 0.05 2.61 2.25 ± 0.03 100% Modulus MPa 0.77 ± 0.06 1.00 ±0.02 0.10 ± 0.03 3.21 ± 0.07 2.90 ± 0.05 3.06 2.61 ± 0.03 Stress @ BreakMPa 0.81 ± 0.13 1.14 ± 0.03 1.44 ± 0.11 6.27 ± 0.23 5.65 ± 0.19 5.375.47 ± 0.25 Strain @ Break % 112 ± 27  127 ± 2.1  83.5 ± 9.4  473 ± 27 414 ± 19  414 457 ± 17 

TABLE 10A Example# Comp P Comp Q Comp R Comp S Comp T Comp O Comp UPolymer 8407 8407 8407 8407 8407 8407 8407 Polymer PHR 100 100 100 100100 100 100 Stearic Acid PHR 0.00 0.13 0.19 0.25 0.75 1.50 2.38 Zn OxidePHR 0.00 0.42 0.63 0.83 2.50 5.00 7.92 1,3-DMB PHR 0.00 0.08 0.13 0.170.50 1.00 1.58 VAROX DBPH-50 0 0.5 0.75 1 3 6 9.5 PHR Polymer wt %100.00 98.89 98.34 97.80 93.68 88.11 82.39 Stearic Acid wt % 0.00 0.120.18 0.24 0.70 1.32 1.96 Zn Oxide wt % 0.00 0.41 0.61 0.81 2.34 4.416.52 1,3-DMB wt % 0.00 0.08 0.12 0.16 0.47 0.88 1.30 VAROX DBPH-50 wt %0.00 0.49 0.74 0.98 2.81 5.29 7.83

TABLE 10B Example# Comp W Inv 9A Inv 10A Inv 11A Inv 12A Inv 8A Inv 13APolymer MP3 MP3 MP3 MP3 MP3 MP3 MP3 Polymer PHR 100 100 100 100 100 100100 Stearic Acid PHR 0.00 0.13 0.19 0.25 0.75 1.50 2.38 Zn Oxide PHR0.00 0.42 0.63 0.83 2.50 5.00 7.92 1,3-DMB PHR 0.00 0.08 0.13 0.17 0.501.00 1.58 VAROX DBPH-50 0 0.5 0.75 1 3 6 9.5 PHR Polymer wt % 100.0098.89 98.34 97.80 93.68 88.11 82.39 Stearic Acid wt % 0.00 0.12 0.180.24 0.70 1.32 1.96 Zn Oxide wt % 0.00 0.41 0.61 0.81 2.34 4.41 6.521,3-DMB wt % 0.00 0.08 0.12 0.16 0.47 0.88 1.30 VAROX DBPH-50 wt % 0.000.49 0.74 0.98 2.81 5.29 7.83

TABLE 11A Example# Comp P Comp Q Comp R Comp S Comp T Comp O Comp UPolymer 8407 8407 8407 8407 8407 8407 8407 ML, [dNm] — 0.006 0.014 0.0080.018 0.027 0.051 MH, [dNm] — 0.145 0.243 0.412 2.077 4.662 7.257 MH-ML,[dNm] — 0.14 0.23 0.40 2.06 4.64 7.21 ts1, [min] — — — — 3.45 1.30 0.72ts2, [min] — — — — 15.25 2.45 1.30 t10, [min] — 0.70 0.97 0.88 0.88 0.690.56 t50, [min] — 4.10 4.02 3.94 3.55 2.86 2.32 t90, [min] — 11.40 11.2911.24 9.59 8.07 6.77 t95, [min] — 18.00 13.00 15.00 12.00 10.00 9.00Rate of Cure (dNm/min) — 0.01 0.02 0.04 0.24 0.63 1.16 RPA Tan Delta @MH — 1.19 0.93 0.29 0.21 0.08 0.05 Shore A Hardness 67 — — — 72 72 73Stress @ Break, MPa 4.3 7.2 4.6 4.9 8.2 5.5 5.3 Strain @ Break, % 9351135 855 767 865 457 326 C-Tear, N/mm 26 29 30 30 30 26 25 CompressionSet, 100° C. (%) — — — — 46 21 8

TABLE 11B Example# Comp W Inv 9A Inv 10A Inv 11A Inv 12A Inv 8A Inv 13APolymer MP3 MP3 MP3 MP3 MP3 MP3 MP3 ML, [dNm] 0.000 0.006 0.006 −0.0020.016 0.022 0.073 MH, [dNm] 0.016 3.701 4.448 4.907 8.220 10.091 11.599MH-ML, [dNm] 0.02 3.70 4.44 4.91 8.20 10.07 11.53 ts1, [min] — 2.46 1.721.45 0.71 0.53 0.43 ts2, [min] — 4.14 2.68 2.21 0.97 0.69 0.55 t10,[min] — 1.51 1.19 1.04 0.66 0.52 0.44 t50, [min] — 3.85 2.92 2.60 1.631.31 1.16 t90, [min] — 9.78 7.40 6.80 5.04 4.80 4.58 t95, [min] — 13.009.70 9.00 6.80 6.70 6.50 Rate of Cure (dNm/min) — 0.45 0.72 0.85 1.872.35 2.78 RPA Tan Delta @ MH 2.75 0.21 0.15 0.13 0.07 0.04 0.04 Shore AHardness 74 — — — 75 75 77 Stress @ Break, MPa 8.1 18.8 14.9 13.6 6.75.2 6.3 Strain @ Break, % 1293 1014 870 867 490 325 291 C-Tear, N/mm 3139 36 37 32 29 26 Compression Set, 100° C. (%) — — — 44 15 8 5

As seen in the tables, the inventive formulations exhibited improvedcrosslinking performance (such as increases in MH-ML and faster rate ofcure) compared to the relevant comparative examples, while alsomaintaining or improving upon physical properties. The followingdiscussion with reference to the figures provides a further explanation.

In Table 11, with the inventive examples a higher degree of cure, asindicated by higher MH-ML, was achieved at a lower peroxide level. Lowerperoxide is beneficial for reducing cost of the formulation, andreducing level of peroxide by-products (volatile organic compounds, odorspecies) for example. Use of lower peroxide with inventive resins alsoprovides scorch resistance as indicated by longer t10. ComparativeExamples O-U are based on ENGAGE 8407. Comparative W is uncured MP3polymer. Inventive 8A-13A are peroxide cured compositions based on MP3.The overall peroxide range used was the same (0.5-9.5 PHR). Theseexamples show that lower peroxide level can be used to achieve a similarMH-ML for the inventive examples. For example, the highest MH-ML with8407 was 7.21 dNm for Comp U at 9.5 PHR peroxide, whereas a similarMH-ML was achieved in Inv. 12A using MP3 and 3 PHR peroxide. Higherperoxide levels resulting in even higher MH-ML (Inv. 8A and 13A), levelsthat could not be achieved with 8407 at the maximum of 9.5 PHR peroxideused. At such high levels of peroxide there is significant gasgeneration due to the peroxide byproducts which can result in defects inmolded cured parts. Comparing Comp U to Inv 12A with similar MH-ML, Inv12A has better scorch resistance (greater t10) but faster cure (lessert95), and greater tensile strength, elongation at break, and tearstrength. Comparing Comp T to Inv 11A, Inv 11A has higher MH-ML, fastercure rate, higher stress at break, higher tear strength, lower tandelta, and similar compression set, while using less peroxide.Meanwhile, Inv 12A (3 PHR peroxide), Inv 8A (6 PHR peroxide) and Inv 13A(9.5 PHR peroxide) have lower compression set and tan delta than Comp T(3 PHR peroxide), Comp 0 (6 PHR peroxide) and Comp U (9.5 PHR peroxide),respectively when compared at the same peroxide level.

FIG. 5 shows that an inventive ethylene/propylene unsaturated polymerallows for significantly better crosslinking performance compared to asaturated ethylene/propylene polymer, when both polymers have about thesame melt index, are used in the same cure package, and are cured underthe same conditions.

FIG. 6 shows that an inventive ethylene/1-octene unsaturated polymerallows for significantly better crosslinking performance compared to asaturated ethylene/1-octene polymer, when both polymers have about thesame melt index, are used in the same cure package, and are cured underthe same conditions.

FIG. 7 surprisingly shows that an inventive ethylene/propyleneunsaturated polymer allows for better crosslinking performance comparedto some EPDM polymers having unsaturations when the same cure packageand same cure conditions are used. While, Inv. 1A did not cure as wellas the 8.8 ENB comparative, it did cure slightly better than the 2.4 ENBcomparative. This is surprising as the inventive unsaturated polymerhaving unsaturations at only end, rather than along the polymerbackbone, shows higher degree of curing, higher crosslinking density,and faster rate of cure compared to an EPDM polymers having about twicethe number of unsaturations. In other words the inventive unsaturatedpolymer shows better crosslinking performance compared to an EPDMpolymer with more unsaturations per 1000 carbons that come from apendant diene.

FIG. 8 shows that inventive ethylene/1-octene telechelic polymers allowfor better crosslinking performance compared to saturatedethylene/1-octene polymers.

Accordingly, the present disclosure provides for a novel low molecularweight unsaturated polyolefin that can be crosslinked efficiently andprovides good mechanical properties, thermal and UV stability.

What is claimed is:
 1. A curable composition comprising (A) a polyolefincomponent and (B) a curing component comprising a cross-linking agent,wherein the (A) polyolefin component comprises an unsaturated polyolefinof the formula A¹L¹, and wherein: L¹ is a polyolefin; A¹ is selectedfrom the group consisting of a vinyl group, a vinylidene group of theformula CH₂═C(Y¹)—, a vinylene group of the formula Y¹CH═CH—, a mixtureof a vinyl group and a vinylene group of the formula Y¹CH═CH—, a mixtureof a vinyl group and a vinylidene group of the formula CH₂═C(Y¹)—, amixture of a vinylidene group of the formula CH₂═C(Y¹)— and a vinylenegroup of the formula Y¹CH═CH—, and a mixture of a vinyl group, avinylidene group of the formula CH₂═C(Y¹)—, and a vinylene group of theformula Y¹CH═CH—; and Y¹ at each occurrence independently is a C₁ to C₃₀hydrocarbyl group.
 2. The composition of claim 1, wherein the (A)polyolefin component further comprises a telechelic polyolefin of theformula A¹L¹L²A², wherein: L² is a C₁ to C₃₂ hydrocarbylene group; andA² is a hydrocarbyl group comprising a hindered double bond.
 3. Thecomposition of any of the preceding claims, wherein the formulationcomprises from 80 wt % to 99.99 wt % of the (A) polyolefin component andfrom 0.01 wt % to 20 wt % of the (B) curing component comprising thecross-linking agent.
 4. The composition of any of the preceding claims,wherein L¹ is an ethylene/alpha-olefin copolymer comprising unitsderived from ethylene and a C₃ to C₃₀ alpha-olefin.
 5. The compositionof any of the preceding claims, wherein the C₃ to C₃₀ alpha-olefin isselected from the group consisting of propylene, 1-butene, 1-hexene, and1-octene.
 6. The composition of any of the preceding claims, wherein thehindered double bond is selected from the group consisting of the doublebond of a vinylidene group, the double bond of a vinylene group, thedouble bond of a trisubstituted alkene, and the double bond of a vinylgroup attached to a branched alpha carbon.
 7. The composition of any ofthe preceding claims, wherein A² a C₃ to C₃₀ cyclic hydrocarbyl group ora C₃ to C₃₀ acyclic hydrocarbyl group.
 8. The composition of any of thepreceding claims, wherein A² is selected from the group consisting of anunsubstituted cycloalkene, an alkyl-substituted cycloalkene, and anacyclic alkyl group.
 9. The composition of any of the preceding claims,wherein A² is selected from the group consisting of:

wherein the endocyclic double bond in (AC) and (AF) may be between anytwo adjacent carbon atoms that are ring members, and wherein the pendantmethyl group of (AF) may be connected to any carbon atom that is a ringmember.
 10. The composition of any of the preceding claims, wherein eachof the unsaturated polyolefin of the formula A¹L¹ and the telechelicpolyolefin of the formula A¹L¹L²A² in the (A) polyolefin componentcomprises a weight average molecular weight (Mw) range from 1,000 to1,000,000 g/mol.
 11. The curable composition of any of preceding claims,wherein L¹ of the unsaturated polyolefin of the formula A¹L¹ iscovalently bonded to A¹ through a carbon-carbon single bond.
 12. Thecurable composition of any of claims 2-11, wherein L¹ of the telechelicpolyolefin of the formula A¹L¹L²A² is covalently bonded to each of A¹and L² through carbon-carbon single bonds, and wherein L² of thetelechelic polyolefin of the formula A¹L¹L²A² is covalently bonded to A²through a carbon-carbon single bond.
 13. The composition of any of thepreceding claims, wherein the (b) curing component further comprises aco-agent.
 14. The composition of any of the preceding claims furthercomprising from 0 to 10 wt % of (C) an additive component.
 15. Thecomposition of any of the preceding claims, wherein the (C) additivecomponent comprises zinc oxide and/or stearic acid.